Leuco polymers as bluing agents in laundry care compositions

ABSTRACT

A leuco polymer comprising an alkoxylated polyethyleneimine covalently bound to a leuco moiety, wherein at least a first portion of nitrogen atoms of the alkoxylated polyethyleneimine have covalently bound thereto a leuco moiety; at least a second portion of nitrogen atoms of the alkoxylated polyethyleneimine have covalently bound thereto a moiety selected from the group consisting of oxyalkylene moieties, polyoxyalkylene moieties, and mixtures thereof; and at least a third portion of nitrogen atoms of the alkoxylated polyethyleneimine have covalently bound thereto a moiety selected from the group consisting of an alkylene chain, an alkylene chain having covalently bound thereto a phenyl or naphthyl group, and mixtures thereof. Methods of making the leuco polymer, laundry care compositions comprising the leuco polymer and methods of treating textiles with such laundry care compositions.

TECHNICAL FIELD

This application describes laundry care compositions that contain leucopolymers and their use in the laundering of textile articles. Thesetypes of leuco polymers are provided in a stable, substantiallycolorless state and then may be transformed to an intense colored stateupon exposure to certain physical or chemical changes such as, forexample, exposure to oxygen, ion addition, exposure to light, and thelike. The laundry care compositions containing the leuco polymers aredesigned to enhance the apparent or visually perceived whiteness of, orto impart a desired hue to, textile articles washed or otherwise treatedwith the laundry care composition.

BACKGROUND

As textile substrates age, their color tends to fade or yellow due toexposure to light, air, soil, and natural degradation of the fibers thatcomprise the substrates. As such, to visually enhance these textilesubstrates and counteract the fading and yellowing the use of polymericcolorants for coloring consumer products has become well known in theprior art. For example, it is well known to use whitening agents, eitheroptical brighteners or bluing agents, in textile applications. However,traditional whitening agents when used at levels providing consumernoticeable whiteness benefits may either adversely impact finishedproduct aesthetics, or if highly depositing, have issues with build upover time and over hueing.

Leuco dyes are also known in the prior art to exhibit a change from acolorless or slightly colored state to a colored state upon exposure tospecific chemical or physical triggers. The change in coloration thatoccurs is typically visually perceptible to the human eye. All existingcompounds have some absorbance in the visible light region (400-750 nm),and thus more or less have some color. In this invention, a dye isconsidered as a “leuco dye” if it did not render a significant color atits application concentration and conditions, but renders a significantcolor in its triggered form. The color change upon triggering stems fromthe change of the molar attenuation coefficient (also known as molarextinction coefficient, molar absorption coefficient, and/or molarabsorptivity in some literatures) of the leuco dye molecule in the400-750 nm range, preferably in the 500-650 nm range, and mostpreferably in the 530-620 nm range. The increase of the molarattenuation coefficient of a leuco dye before and after the triggeringshould be bigger than 50%, more preferably bigger than 200%, and mostpreferably bigger than 500%.

As such, there remains a need for an effective whitening agent thatdeposits to provide the desired whiteness benefit yet does not adverselyimpact finished product aesthetics or cause over hueing after multiplewashes.

It has now surprisingly been found that the presently claimed leucopolymers provide the desired consumer whiteness benefit, without adverseeffects.

SUMMARY OF THE INVENTION

In a first embodiment, the invention provides a leuco polymer thatincludes an alkoxylated polyethyleneimine covalently bound to a leucomoiety. At least a first portion of nitrogen atoms of the alkoxylatedpolyethyleneimine have covalently bound thereto a leuco moiety; at leasta second portion of nitrogen atoms of the alkoxylated polyethyleneiminehave covalently bound thereto a moiety selected from the groupconsisting of oxyalkylene moieties, polyoxyalkylene moieties, andmixtures thereof; and at least a third portion of nitrogen atoms of thealkoxylated polyethyleneimine have covalently bound thereto a moietyselected from the group consisting of an alkylene chain, an alkylenechain having covalently bound thereto a phenyl or naphthyl group, andmixtures thereof.

In a second embodiment, the invention provides a laundry carecomposition comprising (a) laundry care active, and (b) a leuco polymerthat includes an alkoxylated polyethyleneimine covalently bound to aleuco moiety. At least a first portion of nitrogen atoms of thealkoxylated polyethyleneimine have covalently bound thereto a leucomoiety; at least a second portion of nitrogen atoms of the alkoxylatedpolyethyleneimine have covalently bound thereto a moiety selected fromthe group consisting of oxyalkylene moieties, polyoxyalkylene moieties,and mixtures thereof; and at least a third portion of nitrogen atoms ofthe alkoxylated polyethyleneimine have covalently bound thereto a moietyselected from the group consisting of an alkylene chain, an alkylenechain having covalently bound thereto a phenyl or naphthyl group, andmixtures thereof.

In a third embodiment, the invention provides a domestic method oftreating a textile material, the method comprising the steps of (a)treating the textile material with an aqueous solution of a leucopolymer as described herein, (b) optionally, rinsing the textilematerial, and (c) drying the textile material.

DETAILED DESCRIPTION

Definitions

As used herein, the term “alkoxy” is intended to include C₁-C₈ alkoxyand alkoxy derivatives of polyols having repeating units such asbutylene oxide, glycidol oxide, ethylene oxide or propylene oxide.

As used herein, the interchangeable terms “alkyleneoxy” and“oxyalkylene,” and the interchangeable terms “polyalkyleneoxy” and“polyoxyalkylene,” generally refer to molecular structures containingone or more than one, respectively, of the following repeating units:—C₂H₄O—, —C₃H₆O—, —C₄H₈O—, and any combinations thereof. Non-limitingstructures corresponding to these groups include —CH₂CH₂O—,—CH₂CH₂CH₂O—, —CH₂CH₂CH₂CH₂O—, —CH₂CH(CH₃)O—, and —CH₂CH(CH₂CH₃)O—, forexample. Furthermore, the polyoxyalkylene constituent may be selectedfrom the group consisting of one or more monomers selected from a C₂₋₂₀alkyleneoxy group, a glycidyl group, or mixtures thereof.

The terms “ethylene oxide,” “propylene oxide” and “butylene oxide” maybe shown herein by their typical designation of “EO,” “PO” and “BO,”respectively.

As used herein, the terms “alkyl” and “alkyl capped” are intended tomean any univalent group formed by removing a hydrogen atom from asubstituted or unsubstituted hydrocarbon. Non-limiting examples includehydrocarbyl moieties which are branched or unbranched, substituted orunsubstituted including C₁-C₁₈ alkyl groups, and in one aspect, C₁-C₆alkyl groups.

As used herein, unless otherwise specified, the term “aryl” is intendedto include C₃-C₁₂ aryl groups. The term “aryl” refers to bothcarbocyclic and heterocyclic aryl groups.

As used herein, the term “alkaryl” refers to any alkyl-substituted arylsubstituents and aryl-substituted alkyl substituents. More specifically,the term is intended to refer to C7-16 alkyl-substituted arylsubstituents and C7-16 aryl substituted alkyl substituents which may ormay not comprise additional substituents.

As used herein, the term “detergent composition” is a sub-set of laundrycare composition and includes cleaning compositions including but notlimited to products for laundering fabrics. Such compositions may bepre-treatment composition for use prior to a washing step or may berinse added compositions, as well as cleaning auxiliaries, such asbleach additives and “stain-stick” or pre-treat types.

As used herein, the term “laundry care composition” includes, unlessotherwise indicated, granular, powder, liquid, gel, paste, unit dose,bar form and/or flake type washing agents and/or fabric treatmentcompositions, including but not limited to products for launderingfabrics, fabric softening compositions, fabric enhancing compositions,fabric freshening compositions, and other products for the care andmaintenance of fabrics, and combinations thereof. Such compositions maybe pre-treatment compositions for use prior to a washing step or may berinse added compositions, as well as cleaning auxiliaries, such asbleach additives and/or “stain-stick” or pre-treat compositions orsubstrate-laden products such as dryer added sheets.

As used herein, the term “leuco” (as used in reference to, for example,a compound, moiety, radical, dye, monomer, fragment, or polymer) refersto an entity (e.g., organic compound or portion thereof) that, uponexposure to specific chemical or physical triggers, undergoes one ormore chemical and/or physical changes that results in a shift from afirst color state (e.g., uncolored or substantially colorless) to asecond more highly colored state. Suitable chemical or physical triggersinclude, but are not limited to, oxidation, pH change, temperaturechange, and changes in electromagnetic radiation (e.g., light) exposure.Suitable chemical or physical changes that occur in the leuco entityinclude, but are not limited to, oxidation and non-oxidative changes,such as intramolecular cyclization. Thus, in one aspect, a suitableleuco entity can be a reversibly reduced form of a chromophore. In oneaspect, the leuco moiety preferably comprises at least a first and asecond π-system capable of being converted into a third combinedconjugated π-system incorporating said first and second π-systems uponexposure to one or more of the chemical and/or physical triggersdescribed above.

As used herein, the terms “leuco composition” or “leuco colorantcomposition” refers to a composition comprising at least two leucocompounds having independently selected structures as described infurther detail herein.

As used herein “average molecular weight” of the leuco colorant isreported as a weight average molecular weight, as determined by itsmolecular weight distribution: as a consequence of their manufacturingprocess, the leuco colorants disclosed herein may contain a distributionof repeating units in their polymeric moiety.

As used herein, the terms “maximum extinction coefficient” and “maximummolar extinction coefficient” are intended to describe the molarextinction coefficient at the wavelength of maximum absorption (alsoreferred to herein as the maximum wavelength), in the range of 400nanometers to 750 nanometers.

As used herein, the term “first color” is used to refer to the color ofthe laundry care composition before triggering, and is intended toinclude any color, including colorless and substantially colorless.

As used herein, the term “second color” is used to refer to the color ofthe laundry care composition after triggering, and is intended toinclude any color that is distinguishable, either through visualinspection or the use of analytical techniques such asspectrophotometric analysis, from the first color of the laundry carecomposition.

As used herein, the term “converting agent” refers to any oxidizingagent as known in the art other than molecular oxygen in any of itsknown forms (singlet and triplet states).

As used herein, the term “triggering agent” refers to a reactantsuitable for converting the leuco composition from a colorless orsubstantially colorless state to a colored state.

As used herein, the term “whitening agent” refers to a dye or a leucocolorant that may form a dye once triggered that when on white cottonprovides a hue to the cloth with a relative hue angle of 210 to 345, oreven a relative hue angle of 240 to 320, or even a relative hue angle of250 to 300 (e.g., 250 to 290).

As used herein, “cellulosic substrates” are intended to include anysubstrate which comprises at least a majority by weight of cellulose.Cellulose may be found in wood, cotton, linen, jute, and hemp.Cellulosic substrates may be in the form of powders, fibers, pulp andarticles formed from powders, fibers and pulp. Cellulosic fibers,include, without limitation, cotton, rayon (regenerated cellulose),acetate (cellulose acetate), triacetate (cellulose triacetate), andmixtures thereof. Articles formed from cellulosic fibers include textilearticles such as fabrics. Articles formed from pulp include paper.

As used herein, articles such as “a” and “an” when used in a claim, areunderstood to mean one or more of what is claimed or described.

As used herein, the terms “include/s” and “including” are meant to benon-limiting.

As used herein, the term “solid” includes granular, powder, bar andtablet product forms.

As used herein, the term “fluid” includes liquid, gel, paste and gasproduct forms.

The test methods disclosed in the Test Methods Section of the presentapplication should be used to determine the respective values of theparameters of Applicants' inventions.

Unless otherwise noted, all component or composition levels are inreference to the active portion of that component or composition, andare exclusive of impurities, for example, residual solvents orby-products, which may be present in commercially available sources ofsuch components or compositions.

All percentages and ratios are calculated by weight unless otherwiseindicated. All percentages and ratios are calculated based on the totalcomposition unless otherwise indicated.

As used herein, the term “nucleophile” refers to an organic compoundcomprising at least one nucleophilic moiety.

As used herein, the term “nucleophilic moiety” is the part of an organiccompound that provides a pair of electrons to form a new covalent bond.Preferred nucleophilic moieties are portions of organic compoundswherein a resonance structure can be drawn that places a pair ofelectrons on one of the following atoms: carbon, nitrogen, oxygen, orsulfur. Suitable nucleophilic moieties include but are not limited to aprimary amine, a secondary amine, a tertiary amine, a hydroxy group, asulfhydryl group, an enolate, and an eneamine.

As used herein, the term “electrophile” refers to an organic compoundcomprising at least one electrophilic moiety.

As used herein, the term “electrophilic moiety” is the part of anorganic compound that accepts a pair of electrons to form a new covalentbond.

As used herein, the term “leuco polymer” refers to an oligomeric orpolymeric compound comprising at least one leuco moiety.

As used herein, the term “reactive leuco compound(s)” refers to acompound comprising at least one reactive moiety covalently bound to theleuco moiety. A compound that comprises at least one leuco moiety and atleast one electrophilic group is an equivalent description of a“reactive leuco compound(s)” and is used interchangeably herein.

In one aspect, the molar extinction coefficient of said second coloredstate at the maximum absorbance in the wavelength in the range 200 to1,000 nm (more preferably 400 to 750 nm) is preferably at least fivetimes, more preferably 10 times, even more preferably 25 times, mostpreferably at least 50 times the molar extinction coefficient of saidfirst color state at the wavelength of the maximum absorbance of thesecond colored state. Preferably, the molar extinction coefficient ofsaid second colored state at the maximum absorbance in the wavelength inthe range 200 to 1,000 nm (more preferably 400 to 750 nm) is at leastfive times, preferably 10 times, even more preferably 25 times, mostpreferably at least 50 times the maximum molar extinction coefficient ofsaid first color state in the corresponding wavelength range. Anordinarily skilled artisan will realize that these ratios may be muchhigher. For example, the first color state may have a maximum molarextinction coefficient in the wavelength range from 400 to 750 nm of aslittle as 10 M⁻¹ cm⁻¹, and the second colored state may have a maximummolar extinction coefficient in the wavelength range from 400 to 750 nmof as much as 80,000 M⁻¹ cm⁻¹ or more, in which case the ratio of theextinction coefficients would be 8,000:1 or more.

In one aspect, the maximum molar extinction coefficient of said firstcolor state at a wavelength in the range 400 to 750 nm is less than 1000M⁻¹ cm⁻¹, and the maximum molar extinction coefficient of said secondcolored state at a wavelength in the range 400 to 750 nm is more than5,000 M⁻¹ cm⁻¹, preferably more than 10,000, 25,000, 50,000 or even100,000 M⁻¹ cm⁻¹. A skilled artisan will recognize and appreciate that apolymer comprising more than one leuco moiety may have a significantlyhigher maximum molar extinction coefficient in the first color state(e.g., due to the additive effect of a multiplicity of leuco moieties orthe presence of one or more leuco moieties converted to the secondcolored state). Where more than one leuco moiety is attached to amolecule, the maximum molar extinction coefficient of said second colorstate may be more than n×□ where n is the number of leuco moieties plusoxidized leuco moieties present on the molecule, and □ is selected from5,000 M⁻¹ cm⁻¹, preferably more than 10,000, 25,000, 50,000 or even100,000 M⁻¹ cm⁻¹. Thus for a molecule that has two leuco moieties, themaximum molar extinction coefficient of said second color state may bemore than 10,000 M⁻¹ cm⁻¹, preferably more than 20,000, 50,000, 100,000or even 200,000 M⁻¹ cm⁻¹. While n could theoretically be any integer,one skilled in the art appreciates that n will typically be from 1 to100, more preferably 1 to 50, 1 to 25, 1 to 10 or even 1 to 5.

In one preferred embodiment, the leuco entity upon conversion to thesecond more highly colored state provides to white substrates a colorwith a relative hue angle of 210 to 345, or even a relative hue angle of240 to 320, or even a relative hue angle of 250 to 300 (e.g., 250 to290). The relative hue angle can be determined by any suitable method asknown in the art. However, preferably it may be determined as describedin further detail herein with respect to deposition of the leuco entityon cotton relative to cotton absent any leuco entity.

The present invention relates to a class of leuco colorants that may beuseful for use in laundry care compositions, such as liquid laundrydetergent, to provide a hue to whiten textile substrates. Leucocolorants are compounds that are essentially colorless or only lightlycolored but are capable of developing an intense color upon activation.One advantage of using leuco compounds in laundry care compositions isthat such compounds, being colorless until activated, allow the laundrycare composition to exhibit its own color. The leuco colorant generallydoes not alter the primary color of the laundry care composition. Thus,manufacturers of such compositions can formulate a color that is mostattractive to consumers without concern for added ingredients, such asbluing agents, affecting the final color value of the composition.

As noted above, the invention provides a leuco polymer that includes analkoxylated polyethyleneimine covalently bound to a leuco moiety. Atleast a first portion of nitrogen atoms of the alkoxylatedpolyethyleneimine have covalently bound thereto a leuco moiety; at leasta second portion of nitrogen atoms of the alkoxylated polyethyleneiminehave covalently bound thereto a moiety selected from the groupconsisting of oxyalkylene moieties, polyoxyalkylene moieties, andmixtures thereof; and at least a third portion of nitrogen atoms of thealkoxylated polyethyleneimine have covalently bound thereto a moietyselected from the group consisting of an alkylene chain, an alkylenechain having covalently bound thereto a phenyl or naphthyl group, andmixtures thereof.

The alkoxylated polyethylenelmine leuco polymers of the instantinvention give enhanced performance in whitening textiles during laundryprocesses. The alkoxylated polyethylenelmine leuco polymers arepreferably used with non-alkylated alkoxylated polyethylenelmine leucopolymers.

The mixture may be provided by alkylating PEI with less than one moleequivalent of an alkylating agent followed by covalent attachment of aleuco moiety and alkoxylation. Conversely, alkoxylated polyethylenelmineleuco polymers may be mixed with non-alkylated alkoxylatedpolyethylenelmine leuco polymers.

Preferably the mol ratio of non-alkylated alkoxylated polyethylenelmineleuco polymers to alkoxylated polyethylenelmine leuco polymers is from10:1 to 1:100, most preferably 5:1 to 1:5.

Preferably the PEI has from 6 to 100 Nitrogen atoms, more preferably 12to 40, even more preferably from 18 to 36.

Preferably the PEI before reaction with the alkoxy or alkyl moietiescontains at least three primary or secondary amines.

Alkylation is the covalent bonding of an alkyl group to thepolyethyleneimine. Preferably the alkyl group is C₁ to C₈, branched,linear or cyclic, most preferably methyl or ethyl. The alkyl group doesnot have an aryl substituent but may carry non-aromatic substituents.The alkylation is preferably carried out by treating the amine(s) of thePEI with an electrophilic alkylation agent.

Preferred common alkylating agents include dialkyl sulphates (especiallydimethyl and diethyl sulphates), alkyl bromides and iodides, alkyltosylates and the like.

PEI may be alkylated using a wide variety of alkylating agents. Suitablealkylating agents include dialkyl sulfates, alcohols, alkyl halides,olefins, and carbonyl compounds. These reactions are described inUllmann's Encyclopedia of Industrial Chemistry, Acylation andAlkylation, Michael Roper, Eugen Gehrer, Thomas Narbeshuber & WolfgangSiegel (John Wiley ISBN: 9783527306732) and in KIRK-OTHMER ENCYCLOPEDIAOF CHEMICAL TECHNOLOGY, Vol 8, DIAMINES AND HIGHER AMINES, ALIPHATIC(John Wiley ISBN: 9780471238966).

Preferably there are one or two mol equivalents of alkyl groups per onemole of PEI.

Alkoxylated PEI are PEI's, where a single or number of amine functionsare reacted with alkoxy moieties to form an alkoxy side chain. Thealkoxy side chains may be formed by reaction of the PEI with an alkyleneoxide, preferably ethylene oxide, propylene oxide or mixtures thereof.

Preferably the alkoxy side chain is added by the reaction of the PEI,with a alkoxy chain, which contains a reactive group that reacts withprimary or secondary amines of the PEI to form a covalent bond. Examplesof reactive groups are selected from epoxides, alkenes, asulfooxyethylsulfonyl reactive group (—SO₂CH₂CH₂OSO₃Na), heterocyclicreactive groups and leaving groups such as tosylate. The heterocyclicreactive groups are preferably nitrogen contains aromatic rings bound toa halogen or an ammonium group, which react with NH₂ or NH groups toform a covalent bond. The halogen is preferred. More preferredheterocylic reactive groups are dichlorotriazinyl,difluorochloropyrimidine, monofluorotrazinyl, monofluorochlorotrazinyl,dichloroquinoxaline, difluorotriazine, monochlorotriazinyl, andtrichloropyrimidine. Preferably the alkoxy chain contains only onereactive group, to avoid cross-linking reactions, and the other chainend is alkyl capped.

The alkoxy chains are preferably selected from ethoxy or propoxy groups.Most preferably ethoxy. Preferably the alkoxy chain contain 5 to 50alkoxyl repeat unit, more preferably 10 to 20.

The alkylated alkoxylated PEI are PEI's, where a single or a number ofamine functions of the PEI, are reacted with one or more alkylcontaining moieties to form an alkyl side and a single or number ofamine functions are reacted with to form an alkoxy side chain.

The polymer are then mixed with reactive leucos under alkalineconditions, preferably pH=10 to 11. Heating to, for example 300-350° K,accelerates the reaction.

The mixture should then be neutralised to pH 7.

The PEI may be alkylated, alkoxylated then mixed with the compoundcomprising a leuco moiety and an electrophilic moiety. The PEI may bealkoxylated then alkylated then mixed with the compound comprising aleuco moiety and an electrophilic moiety. Preferably the PEI isalkylated then mixed with the compound comprising a leuco moiety and anelectrophilic moiety, and then alkoxylated.

The leuco polymers described above are believed to be suitable for usein the treatment of textile materials, such as in domestic launderingprocesses. In particular, it is believed that the leuco polymer willdeposit onto the fibers of the textile material due to the nature of theleuco polymer. Further, once deposited onto the textile material, theleuco polymer can be converted to a colored polymer through theapplication of the appropriate chemical or physical triggers that willconvert the leuco moiety on the polymer to its colored form. Forexample, the leuco polymer can be converted to its colored form uponoxidation of the leuco moiety to the oxidized colorant. By selecting theproper leuco moiety, the leuco polymer can be designed to impart adesired hue to the textile material as the leuco polymer is converted toits colored form. For example, a leuco polymer that exhibits a blue hueupon conversion to its colored form can be used to counteract theyellowing of the textile material to normally occurs due to the passageof time and/or repeated launderings. Thus, in other embodiments, theinvention provides laundry care compositions comprising theabove-described leuco polymer and domestic methods for treating atextile material (e.g., methods for washing an article of laundry orclothing).

Preferably the leuco polymer gives a hue to the cloth with a relativehue angle of 210 to 345, or even a relative hue angle of 240 to 320, oreven a relative hue angle of 250 to 300 (e.g., 250 to 290). The relativehue angle can be determined by any suitable method as known in the art.However, preferably it may be determined as described in further detailherein with respect to deposition of the leuco entity on cotton relativeto cotton absent any leuco entity.

The reactive leuco compound can comprise any suitable leuco moiety asdefined above. In one aspect, the leuco moiety is a univalent orpolyvalent moiety derived by removal of one or more hydrogen atoms froma structure of Formula (I), (II), (III), (IV), or (V) as definedhereinafter. As noted above, the reactive leuco compound(s) present inthe leuco composition comprise at least one reactive moiety covalentlybound to the leuco moiety. The reactive moiety can be any suitableelectrophilic moiety.

Suitable electrophilic moieties are those that are sufficientlyelectrophilic to react with an organic nucleophilic moiety having aresonance structure (contributing structure) in which a lone pair ofelectrons or a negative charge resides on a carbon, nitrogen, oxygen,sulfur, or phosphorus atom within the moiety. Upon reacting, thereactive moiety creates a covalent bond between the leuco moiety and thecompound containing the organic nucleophilic moiety. Preferably, thereactive moiety is sufficiently electrophilic to react with anucleophilic moiety selected from the group consisting of a hydroxygroup, a sulfhydryl group, a cyano group, alkoxy groups, amine groups(primary, secondary, or tertiary amines), carbanions, carboxyl groups,thiocarboxylate groups, thiolate groups, and thiocyanate groups. Inanother preferred embodiment, the reactive moiety is sufficientlyelectrophilic to react with a nucleophilic moiety selected from thegroup consisting of a hydroxy group, a sulfhydryl group, and aminegroups. Suitable reactive moieties include, but are not limited to,those moieties which react with an amine to form a carbamate, a urea, anamide, a sulfonamide, or a higher order amine (such as secondary aminefrom a primary amine, a tertiary amine from a secondary amine, and aquaternary amine from a primary, secondary or tertiary amine viaalkylation). Suitable reactive moieties also include, but are notlimited to, those moieties which react with an alcohol to formcarbonates, carbamates, carboxylic acid esters, sulfonic acid esters, orethers. Suitable reactive moieties also include, but are not limited to,those moieties which react with a sulfhydryl (thiol) to formthiocarbonates, thiocarbamates, and the like. Suitable reactive moietiesinclude, but are not limited to, those illustrated below:

In the structures above, the index n is 0 or 1. When n is 1, reaction ofthe above groups with an amine forms a carbamate, and reaction with analcohol forms a carbonate. When n is 0, the product of reaction with anamine is a carboxylic acid amide, and the product of reaction with analcohol is a carboxylic acid ester. Similar groups suitable for theformation of sulfonic acid esters and amides are well known to thoseskilled in the art. In like manner, alkyl halides and alkyl tosylatesare representative of reactive groups that may react with an amine toform a higher order amine, or with an alcohol to form an ether.

In addition to the more traditional groups that may be used as reactivemoieties, any of the many specialized electrophilic moieties that havebeen employed as anchoring groups for reactive dyes may be profitablyemployed. Reactive dyes consist of a dye chromophore covalently bound toa reactive moiety. These reactive moieties react with nucleophilicmoieties (e.g., primary and secondary amines) to form a covalent bound,preferably by a substitution or addition reaction. Reactive moieties ofthis sort are preferably selected from heterocyclic reactive moietiesand a sulfooxyethylsulfonyl reactive group (—SO₂CH₂CH₂OSO₃Na). Theheterocyclic reactive moieties are preferably nitrogen contains aromaticrings bound to a halogen or an ammonium, which react with nucleophilicmoieties (e.g., primary amines and second amines) of another compound toform a covalent bond. These heterocyclic reactive moieties preferablycontain a halogen, such as chlorine or fluorine. In a preferredembodiment, the reactive moiety preferably is selected from the groupconsisting of sulfooxyethylsulfonyl moieties, vinylsulfonyl moieties,halotriazinyl moieties, quaternary ammoniumtriazinyl moieties,halopyrimidinyl moieties, halopyridazinyl moieties, haloquinoxalinylmoieties, halophthalazinyl moieties, bromoacrlyamidyl moieties, andbenzothiazolyl moieties. More preferred heterocylic reactive moietiesare dichlorotriazinyl, difluorochloropyrimi-dine, monofluorotrazinyl,monofluorochlorotrazinyl, dichloroquinoxaline, difluorotriazine,monochlorotriazinyl, and trichloropyrimidine. Especially preferredheterocylic reactive moieties are:

wherein R¹ is selected from H or alkyl, preferably H; X is selected fromF or Cl; when X═Cl, Z¹ is selected from —Cl, —NR²R³, —OR², —SO₃Na; whenX═F, Z¹ is selected from —NR²R³ wherein R² and R³ are independentlyselected from H, alkyl and aryl groups. Aryl groups are preferablyphenyl and are preferably substituted by —SO₃Na or —SO₂CH₂CH₂OSO₃Na.Alkyl groups are preferably methyl or ethyl. The phenyl groups may befurther substituted with suitable uncharged organic groups, preferablywith a molecular weight lower than 200. Preferred groups include —CH₃,—C₂H₅, and —OCH₃. The alkyl groups may be further substituted withsuitable uncharged organic groups, preferably with a molecular weightlower than 200. Preferred groups include —CH₃, —C₂H₅, —OH, —OCH₃,—OC₂H₄OH. Most preferred heterocylic reactive moieties are selectedfrom:

wherein m=1 or 2, preferably 1.

In another aspect, the reactive moiety is selected from the groupconsisting of:

wherein R³ is —OSO₃X, —OSO₃ ⁻, or —Cl. R⁴ and R⁵ are independentlyselected from —Cl and —Br; R¹ and R2 are independently selected from—Cl, —F, and the radical selected from:

where R¹⁰ is selected from H, —CO₂X where X is hydrogen or a cation ofan alkali or alkaline earth metal or an ammonium.

In one aspect, the reactive leuco compound comprises more than onereactive moiety, preferably two or three. In such embodiments, thereactive moieties can be the same or different.

The polyethylenimine of the leuco polymer can be any suitablepolyethylenimine. In one aspect, the polyethylenimine comprises three ormore amine nitrogen atoms. In another aspect, the polyethyleniminecomprises about 6 to about 1,000,000 amine nitrogen atoms, about 6 to50,000 amine nitrogen atoms, or about 10 to 200 amine nitrogen atoms. Inyet another aspect, the polyethylenimine comprises about 15 to about 45amine nitrogen atoms.

In one aspect, the polyethylenimine used in making the leuco polymercomprises primary amine groups and/or secondary amine groups, both ofwhich contain at least one amine hydrogen atom. In the leuco polymer, aportion of the amine hydrogen atoms present in the startingpolyethylenimine have been replaced with other groups. In one aspect, aportion of the amine hydrogen atoms in the polyethylenimine are replacedwith a moiety selected from the group consisting of 2-hydroxypropyl,1-hydroxypropane-2-yl, and polyalkoxy groups. In one aspect, thepolyalkoxy group comprises alkoxy groups selected from the groupconsisting of ethoxy groups, propoxy groups, and mixtures thereof. Inanother aspect, the polyalkoxy group comprises 3 or more alkoxy groups.In yet another aspect, the polyalkoxy group comprises 3 to about 50alkoxy groups. If polyalkoxy groups are present in the dye polymer, eachpolyalkoxy group can independently terminate with a moiety selected fromthe group consisting of a hydroxyl group and an alkyl group. In oneaspect, at least a portion of any polyalkoxy groups present in the leucopolymer terminate with a methyl group.

In one aspect, about 20 mol. % to about 95 mol. % of amine hydrogenatoms in the polyethylenimine are replaced with 2-hydroxypropyl groups.In another aspect, about 57 mol. % to about 80 mol. % of amine hydrogenatoms in the polyethylenimine are replaced with 2-hydroxypropyl groups.In yet another aspect, about 3 mol. % to about 15 mol. % of aminehydrogen atoms in the polyethylenimine are replaced with polyalkoxygroups. In a more particular aspect, about 20 mol. % to about 95 mol. %of amine hydrogen atoms in the polyethylenimine are replaced with2-hydroxypropyl groups, and about 3 mol. % to about 15 mol. % of aminehydrogen atoms in the polyethylenimine are replaced with polyalkoxygroups. In another more particular aspect, about 57 mol. % to about 80mol. % of amine hydrogen atoms in the polyethylenimine are replaced with2-hydroxypropyl groups, and about 3 mol. % to about 15 mol. % of aminehydrogen atoms in the polyethylenimine are replaced with polyalkoxygroups.

The leuco moiety covalently bound to the polyethylenimine can be anysuitable leuco moiety. Suitable leuco moieties include, but are notlimited to, diarylmethane moieties, triarylmethane moieties, oxazinemoieties, thiazine moieties, hydroquinone moieties, and arylaminophenolmoieties. Thus, in one aspect, the leuco moiety is selected from thegroup consisting of diarylmethane moieties, triarylmethane moieties,oxazine moieties, thiazine moieties, hydroquinone moieties,arylaminophenol moieties, and mixtures thereof.

Suitable diarylmethane leuco moieties for use herein include, but arenot limited to, univalent or polyvalent diarylmethylene moieties capableof forming a second colored state as described herein. Suitable examplesinclude, but are not limited to, moieties derived from Michler'smethane, a diarylmethylene substituted with an —OH group (e.g.,Michler's hydrol) and ethers and esters thereof, a diarylmethylenesubstituted with a photocleavable group, such as a —CN group(bis(para-N,N-dimethyl)phenyl)acetonitrile), and similar such moieties.

In a more particular aspect, the leuco moiety is a univalent orpolyvalent moiety derived by removal of one or more hydrogen atoms froma structure of Formula (I), (II), (III), (IV), or (V) described below:

wherein the ratio of Formula I-V to its oxidized form is at least 1:19,1:9, or 1:3, preferably at least 1:1, more preferably at least 3:1, mostpreferably at least 9:1 or even 19:1.

In the structure of Formula (I), each individual R_(o), R_(m) and R_(p)group on each of rings A, B and C is independently selected from thegroup consisting of hydrogen, deuterium and R⁵; each R⁵ is independentlyselected from the group consisting of halogens, nitro, alkyl,substituted alkyl, aryl, substituted aryl, alkaryl, substituted alkaryl,—(CH₂)_(n)—R¹, —(CH₂)_(n)—NR¹R², —C(O)R¹, —C(O)OR¹, —C(O)O⁻, —C(O)NR¹R²,—OC(O)R¹, —OC(O)OR¹, —OC(O)NR¹R², —S(O)₂R¹, —S(O)₂OR¹, —S(O)₂O⁻,—S(O)₂NR¹R², —NR¹C(O)R², —NR¹C(O)OR², —NR¹C(O)SR², —NR¹C(O)NR²R³, —OR¹,—NR¹R², —P(O)₂R¹, —P(O)(OR¹)₂, —P(O)(OR¹)O⁻, and —P(O)(O⁻)₂, wherein theindex n is an integer from 0 to 4, preferably from 0 to 1, mostpreferably 0; wherein two R_(o) on different A, B and C rings maycombine to form a fused ring of five or more members; when the fusedring is six or more members, two R_(o) on different A, B and C rings maycombine to form an organic linker optionally containing one or moreheteroatoms; in one embodiment two R_(o) on different A, B and C ringscombine to form a heteroatom bridge selected from —O— and —S— creating asix member fused ring; an R_(o) and R_(m) on the same ring or an R_(m)and R_(p) on the same ring may combine to form a fused aliphatic ring orfused aromatic ring either of which may contain heteroatoms; on at leastone of the three rings A, B or C, preferably at least two, morepreferably at least three, most preferably all four of the R_(o) andR_(m) groups are hydrogen, preferably all four R_(o) and R_(m) groups onat least two of the rings A, B and C are hydrogen; in some embodiments,all R_(o) and R_(m) groups on rings A, B and C are hydrogen; preferablyeach R_(p) is independently selected from hydrogen, —OR¹ and —NR′R²; nomore than two, preferably no more than one of R_(p) is hydrogen,preferably none are hydrogen; more preferably at least one, preferablytwo, most preferably all three R_(p) are —NR¹R²; in some embodiments,one or even two of the Rings A, B and C may be replaced with anindependently selected C₃-C₉ heteroaryl ring comprising one or twoheteroatoms independently selected from O, S and N, optionallysubstituted with one or more independently selected R⁵ groups; G isindependently selected from the group consisting of hydrogen, deuterium,C₁-C₁₆ alkoxide, phenoxide, bisphenoxide, nitrite, nitrile, alkyl amine,imidazole, arylamine, polyalkylene oxide, halides, alkylsulfide, arylsulfide, or phosphine oxide; in one aspect the fraction[(deuterium)/(deuterium+hydrogen)] for G is at least 0.20, preferably atleast 0.40, even more preferably at least 0.50 and most preferably atleast 0.60 or even at least 0.80;

wherein any two of R¹, R² and R³ attached to the same heteroatom cancombine to form a ring of five or more members optionally comprising oneor more additional heteroatoms selected from the group consisting of—O—, —NR¹⁵—, and —S—.

In the structures of Formula (II)-(III), wherein e and f areindependently integers from 0 to 4; each R²⁰ and R²¹ is independentlyselected from the group consisting of halogens, a nitro group, alkylgroups, substituted alkyl groups, —NC(O)OR¹, —NC(O)SR¹, —OR¹, and—NR¹R²; each R²⁵ is independently selected from the group consisting ofmonosaccharide moiety, disaccharide moiety, oligosaccharide moiety, andpolysaccharide moiety, —C(O)R¹, —C(O)OR¹, —C(O)NR¹R²; and each R²² andR²³ is independently selected from the group consisting of hydrogen,alkyl groups, and substituted alkyl groups.

In the structure of Formula (IV), R³⁰ is positioned ortho or para to thebridging amine moiety and is selected from the group consisting of —OR³⁸and —NR³⁶R³⁷, each R³⁶ and R³⁷ is independently selected from the groupconsisting of hydrogen, alkyl groups, substituted alkyl groups, arylgroups, substituted aryl groups, acyl groups, R⁴, —C(O)OR¹, —C(O)R¹, and—C(O)NR¹R²; R³⁸ is selected from the group consisting of hydrogen, acylgroups, —C(O)OR¹, —C(O)R¹, and —C(O)NR¹R²; g and h are independentlyintegers from 0 to 4; each R³¹ and R³² is independently selected fromthe group consisting of alkyl groups, substituted alkyl groups, arylgroups, substituted aryl groups, alkaryl, substituted alkaryl,—(CH₂)_(n)—OR¹, —(CH₂)_(n)—NR¹R², —C(O)R¹, —C(O)OR¹, —C(O)O⁻,—C(O)NR¹R², —OC(O)R¹, —OC(O)OR¹, —OC(O)NR¹R², —S(O)₂R¹, —S(O)₂OR¹,—S(O)₂O⁻, —S(O)₂NR¹R², —NR¹C(O)R², —NR¹C(O)OR², —NR¹C(O)SR²,—NR¹C(O)NR²R³, —P(O)₂R¹, —P(O)(OR¹)₂, —P(O)(OR¹)O⁻, and —P(O)(O⁻)₂,wherein the index n is an integer from 0 to 4, preferably from 0 to 1,most preferably 0; —NR³⁴R³⁵ is positioned ortho or para to the bridgingamine moiety and R³⁴ and R³⁵ are independently selected from the groupconsisting of hydrogen, alkyl, substituted alkyl, aryl, substitutedaryl, alkaryl, substituted alkaryl, and R⁴; R³³ is independentlyselected from the group consisting of hydrogen, —S(O)₂R¹, —C(O)N(H)R¹;—C(O)OR¹; and —C(O)R¹; when g is 2 to 4, any two adjacent R³¹ groups maycombine to form a fused ring of five or more members wherein no morethan two of the atoms in the fused ring may be nitrogen atoms.

In the structure of Formula (V), X⁴⁰ is selected from the groupconsisting of an oxygen atom, a sulfur atom, and NR⁴⁵; R⁴⁵ isindependently selected from the group consisting of hydrogen, deuterium,alkyl, substituted alkyl, aryl, substituted aryl, alkaryl, substitutedalkaryl, —S(O)₂OH, —S(O)₂O⁻, —C(O)OR¹, —C(O)R¹, and —C(O)NR¹R²; R⁴⁰ andR⁴¹ are independently selected from the group consisting of—(CH₂)_(n)—OR¹, —(CH₂)_(n)—NR¹R², wherein the index n is an integer from0 to 4, preferably from 0 to 1, most preferably 0; j and k areindependently integers from 0 to 3; R⁴² and R⁴³ are independentlyselected from the group consisting of alkyl, substituted alkyl, aryl,substituted aryl, alkaryl, substituted alkaryl, —S(O)₂R¹, —C(O)NR¹R²,—NC(O)OR¹, —NC(O)SR¹, —C(O)OR¹, —C(O)R¹, —(CH₂)_(n)—O—R¹,—(CH₂)_(n)—NR¹R², wherein the index n is an integer from 0 to 4,preferably from 0 to 1, most preferably 0; R⁴⁴ is —C(O)R¹, —C(O)NR¹R²,and —C(O)OR¹.

In the structures of Formula (I)-(V), wherein any charge present in anyof the preceeding groups is balanced with a suitable independentlyselected internal or external counterion. Suitable independentlyselected external counterions may be cationic or anionic. Examples ofsuitable cations include but are not limited to one or more metalspreferably selected from Group I and Group II, the most preferred ofthese being Na, K, Mg, and Ca, or an organic cation such as iminium,ammonium, and phosphonium. Examples of suitable anions include but arenot limited to: fluoride, chloride, bromide, iodide, perchlorate,hydrogen sulfate, sulfate, aminosulfate, nitrate, dihydrogen phosphate,hydrogen phosphate, phosphate, bicarbonate, carbonate, methosulfate,ethosulfate, cyanate, thiocyanate, tetrachlorozincate, borate,tetrafluoroborate, acetate, chloroacetate, cyanoacetate, hydroxyacetate,aminoacetate, methylaminoacetate, di- and tri-chloroacetate,2-chloro-propionate, 2-hydroxypropionate, glycolate, thioglycolate,thioacetate, phenoxyacetate, trimethylacetate, valerate, palmitate,acrylate, oxalate, malonate, crotonate, succinate, citrate,methylene-bis-thioglycolate, ethylene-bis-iminoacetate,nitrilotriacetate, fumarate, maleate, benzoate, methylbenzoate,chlorobenzoate, dichlorobenzoate, hydroxybenzoate, aminobenzoate,phthalate, terephthalate, indolylacetate, chlorobenzenesulfonate,benzenesulfonate, toluenesulfonate, biphenyl-sulfonate andchlorotoluenesulfonate. Those of ordinary skill in the art are wellaware of different counterions which can be used in place of thoselisted above.

In the structures of Formula (I)-(V), R¹, R², R³, and R¹⁵ areindependently selected from the group consisting of hydrogen, alkyl,substituted alkyl, aryl, substituted aryl, alkaryl, substituted alkaryl,and R⁴; wherein R⁴ is an organic group composed of one or more organicmonomers with said monomer molecular weights ranging from 28 to 500,preferably 43 to 350, even more preferably 43 to 250, wherein theorganic group may be substituted with one or more additional leucocolorant moieties conforming to the structure of Formula I-V. In oneaspect, R⁴ is selected from the group consisting of alkyleneoxy(polyether), oxoalkyleneoxy (polyesters), oxoalkyleneamine (polyamides),epichlorohydrin, quaternized epichlorohydrin, alkyleneamine,hydroxyalkylene, acyloxyalkylene, carboxyalkylene, carboalkoxyalkylene,and sugar. Where any leuco colorant comprises an R⁴ group with three ormore contiguous monomers, that leuco colorant is defined herein as a“polymeric leuco colorant”. One skilled in the art knows that theproperties of a compound with regard to any of a number ofcharacteristic attributes such as solubility, partitioning, deposition,removal, staining, etc., are related to the placement, identity andnumber of such contiguous monomers incorporated therein. The skilledartisan can therefore adjust the placement, identity and number of suchcontiguous monomers to alter any particular attribute in a more or lesspredictable fashion.

The leuco moiety can be covalently bound to the polyethylenimine throughany suitable covalent linkage. In once aspect, the leuco moiety iscovalently bound to an amine nitrogen in the polyethylenimine. In otherwords, the leuco moiety can be covalently bound to the polyethylenimineby replacing an amine hydrogen on the polyethylenimine.

The leuco polymer can comprise any suitable number of leuco moieties. Asnoted above, the leuco polymer comprises at least one leuco moiety. Inone aspect, the leuco polymer comprises a plurality of leuco moieties,each of which is independently selected from the groups described above.In one aspect, the leuco polymer comprises 1 to about 5 leuco moieties.In another aspect, the leuco polymer comprises 1 to about 2 leucomoieties. In one aspect, the leuco moiety can be attached to two or morepolyethylenimines. Preferably, the leuco moiety is only attached to onepolyethylenimine. In another aspect, the leuco moiety comprises about 1wt. % to about 45 wt. % of the leuco polymer. (This weight percentagecan be calculated by dividing the formula mass of the leuco moiety bythe molar mass of the leuco polymer.)

The leuco polymer can also comprise a chromophore moiety covalentlybound to the polyethylenimine. In one aspect, such chromophore moietycan be the colored counterpart to a leuco moiety that is also bound tothe polyethylenimine. For example, the dye polymer can initially havetwo leuco moieties bound to the polyethylenimine, and one of the leucomoieties can convert to the corresponding colored chromophore moiety. Inanother aspect, such chromophore moiety can be different from the leucomoiety bound to the polyethylenimine (i.e., the chromophore moiety isnot the colored counterpart to the leuco moiety bound to thepolyethylenimine).

In one aspect, the leuco polymer can further comprise a red dye moietycovalently bound to the polyethylenimine. If present, such red dyemoiety can be present in any suitable amount. In one aspect, the ratioof red dye moieties to leuco moieties present in the leuco polymer is1:100 to 1:4. The inclusion of the red dye moiety provides a red shadeto the leuco polymer. In one aspect, the red dye moiety preferably is amono-azo dye moiety.

In another aspect, the leuco polymer can be present in a leuco polymercomposition. The leuco polymer composition comprises at least one leucopolymer as described above. In one aspect, the leuco polymer compositioncan also comprise another polyethylenimine polymer. For example, theleuco polymer composition can comprise the virgin polyethyleniminepolymer used to produce the leuco polymer as described above. In anotheraspect, the leuco polymer composition can comprise a polyethyleniminepolymer that is similar in structure to the leuco polymer describedabove but which lacks a leuco moiety. In yet another aspect, the leucopolymer composition can comprise a colored polymer that is produced byconversion of a leuco moiety on a molecule of the leuco polymer to itscorresponding colored chromophore moiety.

The leuco polymer described above can be made by any suitable process.In one aspect, the leuco polymer can be made by: (a) reacting apolyethyleneimine with a reactive leuco compound to produce apolyethyleneimine-leuco intermediate; (b) reacting thepolyethyleneimine-leuco intermediate with propylene oxide to produce apropoxylated polyethyleneimine-leuco intermediate; and (c) reacting thepropoxylated polyethyleneimine-leuco intermediate with an alkylene oxideto produce a leuco polymer. In another aspect, the leuco polymer can bemade by: (a) reacting a polyethyleneimine with propylene oxide toproduce a propoxylated polyethyleneimine intermediate; (b) reacting thepropoxylated polyethyleneimine intermediate with a polyalkoxy compoundto produce an alkoxylated polyethyleneimine intermediate; (c) reactingthe alkoxylated polyethyleneimine intermediate with a reactive leucocompound to produce a leuco polymer.

The polyethylenimine used in the processes described above can be anysuitable polyethylenimine polymer. Suitable polyethylenimines include,but are not limited to, highly branched polyamines characterized byrepeating units having the empirical formula (C₂H₅N)_(n) with amolecular mass of 43.07. Polyethylenimines typically are commerciallyprepared by the acid-catalyzed ring opening of ethylenimine, also knownas aziridine. The ethylenimine starting material typically is preparedthrough sulfuric acid esterification of ethanolamine.

In one aspect, the polyethylenimine comprises three or more aminenitrogen atoms. In another aspect, the polyethylenimine comprises about6 to about 1,000,000 amine nitrogen atoms, about 6 to 50,000 aminenitrogen atoms, or about 10 to 200 amine nitrogen atoms. In yet anotheraspect, the polyethylenimine comprises about 15 to about 45 aminenitrogen atoms.

The polyethylenimine used in making the leuco polymer comprises primaryamine groups and/or secondary amine groups, both of which contain atleast one amine hydrogen atom. In one aspect, the polyethylenimine alsopreferably contains tertiary amine groups. A portion of the amine groupsin the polyethylenimine can be substituted with other groups, such as analkyl group, an alkyl sulfate group, an alkyl aryl group, or an alkylaryl sulfate group.

In the propoxylation step of the processes described above, thepolyethylenimine or intermediate is reacted with propylene oxide toreplace at least a portion of the amine hydrogen atoms with groupsselected from 2-hydroxypropyl, 1-hydroxypropane-2-yl, and mixturesthereof. The polyethylenimine or intermediate can be reacted with anysuitable amount of propylene oxide. In one aspect, the amount ofpropylene oxide used is sufficient to react with and replace 1 mol. % ormore of the amine hydrogen atoms in the polyethylenimine orintermediate. In another aspect, the amount of propylene oxide used issufficient to react with and replace about 20 mol. % to about 95 mol. %of the amine hydrogen atoms in the polyethylenimine or intermediate. Inyet another aspect, the amount of propylene oxide used is sufficient toreact with and replace about 57 mol. % to about 80 mol. % of the aminehydrogen atoms in the polyethylenimine or intermediate.

The polyalkoxy compound used in making the leuco polymer can be anysuitable polyalkoxy compound. In one aspect, the polyalkoxy compoundcomprises alkoxy repeating groups selected from the group consisting ofethoxy groups (—OCH₂CH₂—), propoxy groups (—OCH₂CH₂CH₂—), and mixturesthereof. In one aspect, the polyalkoxy compound comprises 3 or morealkoxy repeating groups. In yet another aspect, the polyalkoxy compoundcomprises 3 to about 50 alkoxy repeating groups. In order to facilitatereaction of the polyalkoxy compound with the polyethylenimine or anintermediate, the polyalkoxy compound typically comprises a reactivegroup (i.e., a group that is reactive to amine hydrogens). Suitablereactive groups for the polyalkoxy compound include, but are not limitedto, epoxides, alkenes, sulfooxyethylsulfonyl groups (e.g.,—SO₂CH₂CH₂OSO₃Na), heterocyclic reactive groups, and leaving groups(e.g., tosylate). In one aspect, the polyalkoxy compound preferablycomprises ethoxy groups. In a more particular aspect, the polyalkoxycompound is a compound of structure (PA1) below

The compound of structure (PA1) is shown with 13 ethoxy groups, butcompounds containing fewer or more ethoxy groups will also be suitablefor use in making the leuco polymer.

In the reaction with the polyalkoxy compound, the polyethylenimine orintermediate is reacted with the polyalkoxy compound to replace one ormore of the amine hydrogen atoms present on the polyethylenimine orintermediate with a polyalkoxy group derived from the polyalkoxycompound. Any suitable amount of polalkoxy compound can be reacted withthe polyethylenimine or intermediate. In one aspect, the amount ofpolyalkoxy compound utilized is sufficient to react with and replace oneof the amine hydrogen atoms on the polyethylenimine or intermediate.

In the step of reacting with the reacting the polyethylenimine orintermediate with the reactive leuco compound, the reactive leucocompound reacts with and replaces an amine hydrogen atom on thepolyethylenimine or intermediate. Any suitable amount of leuco compoundcan be used in this reaction. In one aspect, the molar ratio of reactiveleuco compound to polyethylenimine or intermediate is from about 0.2:1to about 1:1.

In an exemplary embodiment of the processes for making the leucopolymer, a polyethylenimine (PEI1) containing 29 nitrogen atoms, ofwhich 9 are primary (i.e., NH₂), 13 are secondary (i.e., NH), and 7 aretertiary, is reacted with 26 mole equivalents of propylene oxide to givethe structure below (PEI2).

The unsubstituted initial polyethylenimine (PEI1) contained(2×9)+(1×13)=31 amine hydrogens on the primary and secondary nitrogenatoms. When reacted with 26 mol equivalents of propylene oxide,26/31×100=83.9 mol. % of the amine hydrogens of the primary andsecondary nitrogen atoms have been replaced by a 2-hydroxypropyl groupor a 1-hydroxypropane-2-yl group. In the structure of (PEI2), only2-hydroxypropyl groups have been shown for the sake of simplicity.

In this exemplary embodiment, the propoxylated polyethylenimine (PEI2)is then reacted with 1 mole equivalent of the polyalkoxy compound (PA1)to produce the alkoxylated propoxylated intermediate (PEI3)

The alkoxylated propoxylated intermediate (PEI3) is then reacted with 1mole equivalent of a reactive leuco compound, such as a reactive leucocompound of structure (RLC1)

The result of this reaction is a leuco polymer as described above andwhich has the structure of (LP 1)

The leuco polymers described above are believed to be suitable for usein the treatment of textile materials, such as in domestic launderingprocesses. In particular, it is believed that the leuco polymer willdeposit onto the fibers of the textile material due to the nature of thealkoxylated nature of the polyethylenimine polymer. Further, oncedeposited onto the textile material, the leuco polymer can be convertedto a colored polymer through the application of the appropriate chemicalor physical triggers that will convert the leuco moiety on the polymerto its colored form. For example, the leuco polymer (LP1) can beconverted to its colored form upon oxidation of the leuco moiety to ananthraquinone moiety. By selecting the proper leuco moiety, the leucopolymer can be designed to impart a desired hue to the textile materialas the leuco polymer is converted to its colored form. For example, aleuco polymer that exhibits a blue hue upon conversion to its coloredform can be used to counteract the yellowing of the textile material tonormally occurs due to the passage of time and/or repeated launderings.Thus, in other embodiments, the invention provides laundry carecompositions comprising the above-described leuco polymer and domesticmethods for treating a textile material (e.g., methods for washing anarticle of laundry or clothing).

In a fourth embodiment, the invention provides a laundry carecomposition comprising (a) laundry care active, and (b) a leuco polymeras described above. In one aspect, the leuco polymer comprises apolyethylenimine and at least one leuco moiety covalently bound to thepolyethylenimine, wherein the polyethylenimine comprises three or moreamine nitrogen atoms and 1 mol. % or more of amine hydrogen atoms in thepolyethylenimine are replaced with a moiety selected from the groupconsisting of 2-hydroxypropyl, 1-hydroxypropane-2-yl, and polyalkoxygroups.

The leuco polymer present in the laundry care composition can be any ofthe leuco polymers described above in connection with the earlierembodiments of the invention. The leuco polymer can be present in thelaundry care composition in any suitable amount. In one aspect, thelaundry care composition comprises from about 0.001 wt. % to about 2.0wt. %, preferably about 0.05 wt. % to about 0.2 wt. %, of the leucopolymer. In such an embodiment, the laundry care composition cancomprise from about 2 wt. % to about 70 wt. % of surfactant (either asingle surfactant or, more preferably, a combination of surfactantsselected from those discussed below).

Laundry Care Ingredients

Surfactant System

The products of the present invention may comprise from about 0.00 wt %,more typically from about 0.10 to 80% by weight of a surfactant. In oneaspect, such compositions may comprise from about 5% to 50% by weight ofsurfactant. Surfactants utilized can be of the anionic, nonionic,amphoteric, ampholytic, zwitterionic, or cationic type or can comprisecompatible mixtures of these types. Anionic and nonionic surfactants aretypically employed if the fabric care product is a laundry detergent. Onthe other hand, cationic surfactants are typically employed if thefabric care product is a fabric softener.

Anionic Surfactant

Useful anionic surfactants can themselves be of several different types.For example, water-soluble salts of the higher fatty acids, i.e.,“soaps”, are useful anionic surfactants in the compositions herein. Thisincludes alkali metal soaps such as the sodium, potassium, ammonium, andalkylolammonium salts of higher fatty acids containing from about 8 toabout 24 carbon atoms, or even from about 12 to about 18 carbon atoms.Soaps can be made by direct saponification of fats and oils or by theneutralization of free fatty acids. Particularly useful are the sodiumand potassium salts of the mixtures of fatty acids derived from coconutoil and tallow, i.e., sodium or potassium tallow and coconut soap.

Preferred alkyl sulphates are C8-18 alkyl alkoxylated sulphates,preferably a C12-15 alkyl or hydroxyalkyl alkoxylated sulphates.Preferably the alkoxylating group is an ethoxylating group. Typicallythe alkyl alkoxylated sulphate has an average degree of alkoxylationfrom 0.5 to 30 or 20, or from 0.5 to 10. The alkyl group may be branchedor linear. The alkoxylated alkyl sulfate surfactant may be a mixture ofalkoxylated alkyl sulfates, the mixture having an average (arithmeticmean) carbon chain length within the range of about 12 to about 30carbon atoms, or an average carbon chain length of about 12 to about 15carbon atoms, and an average (arithmetic mean) degree of alkoxylation offrom about 1 mol to about 4 mols of ethylene oxide, propylene oxide, ormixtures thereof, or an average (arithmetic mean) degree of alkoxylationof about 1.8 mols of ethylene oxide, propylene oxide, or mixturesthereof. The alkoxylated alkyl sulfate surfactant may have a carbonchain length from about 10 carbon atoms to about 18 carbon atoms, and adegree of alkoxylation of from about 0.1 to about 6 mols of ethyleneoxide, propylene oxide, or mixtures thereof. The alkoxylated alkylsulfate may be alkoxylated with ethylene oxide, propylene oxide, ormixtures thereof. Alkyl ether sulfate surfactants may contain a peakedethoxylate distribution. Specific example include C12-C15 EO 2.5Sulfate, C14-C15 EO 2.5 Sulfate and C12-C15 EO 1.5 Sulfate derived fromNEODOL® alcohols from Shell and C12-C14 EO3 Sulfate, C12-C16 EO3Sulfate, C12-C14 EO2 Sulfate and C12-C14 EO 1 Sulfate derived fromnatural alcohols from Huntsman. The AES may be linear, branched, orcombinations thereof. The alkyl group may be derived from synthetic ornatural alcohols such as those supplied by the tradename Neodol® byShell, Safol®, Lial®, and Isalchem® by Sasol or midcut alcohols derivedfrom vegetable oils such as coconut and palm kernel. Another suitableanionic detersive surfactant is alkyl ether carboxylate, comprising aC10-C26 linear or branched, preferably C10-C20 linear, most preferablyC16-C18 linear alkyl alcohol and from 2 to 20, preferably 7 to 13, morepreferably 8 to 12, most preferably 9.5 to 10.5 ethoxylates. The acidform or salt form, such as sodium or ammonium salt, may be used, and thealkyl chain may contain one cis or trans double bond. Alkyl ethercarboxylic acids are available from Kao (Akypo®), Huntsman (Empicol®)and Clariant (Emulsogen®).

Other useful anionic surfactants can include the alkali metal salts ofalkyl benzene sulfonates, in which the alkyl group contains from about 9to about 15 carbon atoms, in straight chain (linear) or branched chainconfiguration. In some examples, the alkyl group is linear. Such linearalkylbenzene sulfonates are known as “LAS.” In other examples, thelinear alkylbenzene sulfonate may have an average number of carbon atomsin the alkyl group of from about 11 to 14. In a specific example, thelinear straight chain alkylbenzene sulfonates may have an average numberof carbon atoms in the alkyl group of about 11.8 carbon atoms, which maybe abbreviated as C11.8 LAS. Preferred sulphonates are C10-13 alkylbenzene sulphonate. Suitable alkyl benzene sulphonate (LAS) may beobtained, by sulphonating commercially available linear alkyl benzene(LAB); suitable LAB includes low 2-phenyl LAB, such as those supplied bySasol under the tradename Isochem® or those supplied by Petresa underthe tradename Petrelab®, other suitable LAB include high 2-phenyl LAB,such as those supplied by Sasol under the tradename Hyblene®. A suitableanionic detersive surfactant is alkyl benzene sulphonate that isobtained by DETAL catalyzed process, although other synthesis routes,such as HF, may also be suitable. In one aspect a magnesium salt of LASis used. Suitable anionic sulfonate surfactants for use herein includewater-soluble salts of C8-C18 alkyl or hydroxyalkyl sulfonates; C11-C18alkyl benzene sulfonates (LAS), modified alkylbenzene sulfonate (MLAS)as discussed in WO 99/05243, WO 99/05242, WO 99/05244, WO 99/05082, WO99/05084, WO 99/05241, WO 99/07656, WO 00/23549, and WO 00/23548; methylester sulfonate (MES); and alpha-olefin sulfonate (AOS). Those alsoinclude the paraffin sulfonates may be monosulfonates and/ordisulfonates, obtained by sulfonating paraffins of 10 to 20 carbonatoms. The sulfonate surfactant may also include the alkyl glycerylsulfonate surfactants.

Anionic surfactants of the present invention may exist in an acid form,and said acid form may be neutralized to form a surfactant salt which isdesirable for use in the present detergent compositions. Typical agentsfor neutralization include the metal counterion base such as hydroxides,e.g., NaOH or KOH. Further preferred agents for neutralizing anionicsurfactants of the present invention and adjunct anionic surfactants orcosurfactants in their acid forms include ammonia, amines, oralkanolamines. Alkanolamines are preferred. Suitable non-limitingexamples including monoethanolamine, diethanolamine, triethanolamine,and other linear or branched alkanolamines known in the art; forexample, highly preferred alkanolamines include 2-amino-1-propanol,1-aminopropanol, monoisopropanolamine, or 1-amino-3-propanol.

Nonionic Surfactant

Preferably the composition comprises a nonionic detersive surfactant.Suitable nonionic surfactants include alkoxylated fatty alcohols. Thenonionic surfactant may be selected from ethoxylated alcohols andethoxylated alkyl phenols of the formula R(OC2H4),OH, wherein R isselected from the group consisting of aliphatic hydrocarbon radicalscontaining from about 8 to about 15 carbon atoms and alkyl phenylradicals in which the alkyl groups contain from about 8 to about 12carbon atoms, and the average value of n is from about 5 to about 15.Other non-limiting examples of nonionic surfactants useful hereininclude: C8-C18 alkyl ethoxylates, such as, NEODOL® nonionic surfactantsfrom Shell; C6-C12 alkyl phenol alkoxylates where the alkoxylate unitsmay be ethyleneoxy units, propyleneoxy units, or a mixture thereof;C12-C18 alcohol and C6-C12 alkyl phenol condensates with ethyleneoxide/propylene oxide block polymers such as Pluronic® from BASF;C14-C22 mid-chain branched alcohols, BA; C14-C22 mid-chain branchedalkyl alkoxylates, BAE_(X), wherein x is from 1 to 30;alkylpolysaccharides; specifically alkylpolyglycosides; polyhydroxyfatty acid amides; and ether capped poly(oxyalkylated) alcoholsurfactants. Specific example include C12-C15 EO 7 and C14-C15 EO 7NEODOL® nonionic surfactants from Shell, C12-C14 EO 7 and C12-C14 EO 9Surfonic® nonionic surfactants from Huntsman.

Highly preferred nonionic surfactants are the condensation products ofGuerbet alcohols with from 2 to 18 moles, preferably 2 to 15, morepreferably 5-9 of ethylene oxide per mole of alcohol. Suitable nonionicsurfactants include those with the trade name Lutensol® from BASF.Lutensol XP-50 is a Guerbet ethoxylate that contains an average of about5 ethoxy groups. Lutensol XP-80 and containing an average of about 8ethoxy groups. Other suitable non-ionic surfactants for use hereininclude fatty alcohol polyglycol ethers, alkylpolyglucosides and fattyacid glucamides, alkylpolyglucosides based on Guerbet alcohols.

Amphoteric Surfactant

The surfactant system may include amphoteric surfactant, such as amineoxide. Preferred amine oxides are alkyl dimethyl amine oxide or alkylamido propyl dimethyl amine oxide, more preferably alkyl dimethyl amineoxide and especially coco dimethyl amino oxide. Amine oxide may have alinear or mid-branched alkyl moiety.

Ampholytic Surfactants

The surfactant system may comprise an ampholytic surfactant. Specific,non-limiting examples of ampholytic surfactants include: aliphaticderivatives of secondary or tertiary amines, or aliphatic derivatives ofheterocyclic secondary and tertiary amines in which the aliphaticradical can be straight- or branched-chain. One of the aliphaticsubstituents may contain at least about 8 carbon atoms, for example fromabout 8 to about 18 carbon atoms, and at least one contains an anionicwater-solubilizing group, e.g. carboxy, sulfonate, sulfate. See U.S.Pat. No. 3,929,678 at column 19, lines 18-35, for suitable examples ofampholytic surfactants.

Zwitterionic Surfactant

Zwitterionic surfactants are known in the art, and generally includesurfactants which are neutrally charged overall, but carry at least onepositive charged atom/group and at least one negatively chargedatom/group. Examples of zwitterionic surfactants include: derivatives ofsecondary and tertiary amines, derivatives of heterocyclic secondary andtertiary amines, or derivatives of quaternary ammonium, quaternaryphosphonium or tertiary sulfonium compounds. See U.S. Pat. No. 3,929,678at column 19, line 38 through column 22, line 48, for examples ofzwitterionic surfactants; betaines, including alkyl dimethyl betaine andcocodimethyl amidopropyl betaine, C₈ to C₁₈ (for example from C₁₂ toC₁₈) amine oxides and sulfo and hydroxy betaines, such asN-alkyl-N,N-dimethylammino-1-propane sulfonate where the alkyl group canbe C₈ to C₁₈ and in certain embodiments from C₁₀ to C₁₄. A preferredzwitterionic surfactant for use in the present invention is thecocoamidopropyl betaine.

Cationic Surfactants

Examples of cationic surfactants include quaternary ammoniumsurfactants, which can have up to 26 carbon atoms specific. Additionalexamples include a) alkoxylate quaternary ammonium (AQA) surfactants asdiscussed in U.S. Pat. No. 6,136,769; b) dimethyl hydroxyethylquaternary ammonium as discussed in U.S. Pat. No. 6,004,922; c)polyamine cationic surfactants as discussed in WO 98/35002, WO 98/35003,WO 98/35004, WO 98/35005, and WO 98/35006, which is herein incorporatedby reference; d) cationic ester surfactants as discussed in U.S. Pat.Nos. 4,228,042, 4,239,660 4,260,529 and U.S. Pat. No. 6,022,844, whichis herein incorporated by reference; and e) amino surfactants asdiscussed in U.S. Pat. No. 6,221,825 and WO 00/47708, which is hereinincorporated by reference, and specifically amido propyldimethyl amine(APA). Useful cationic surfactants also include those described in U.S.Pat. No. 4,222,905, Cockrell, issued Sep. 16, 1980, and in U.S. Pat. No.4,239,659, Murphy, issued Dec. 16, 1980, both of which are alsoincorporated herein by reference. Quaternary ammonium compounds may bepresent in fabric enhancer compositions, such as fabric softeners, andcomprise quaternary ammonium cations that are positively chargedpolyatomic ions of the structure NR₄ ⁺, where R is an alkyl group or anaryl group.

Adjunct Cleaning Additives

The cleaning compositions of the invention may also contain adjunctcleaning additives. The precise nature of the cleaning adjunct additivesand levels of incorporation thereof will depend on the physical form ofthe cleaning composition, and the precise nature of the cleaningoperation for which it is to be used.

The adjunct cleaning additives may be selected from the group consistingof builders, structurants or thickeners, clay soilremoval/anti-redeposition agents, polymeric soil release agents,polymeric dispersing agents, polymeric grease cleaning agents, enzymes,enzyme stabilizing systems, bleaching compounds, bleaching agents,bleach activators, bleach catalysts, brighteners, dyes, hueing agents,dye transfer inhibiting agents, chelating agents, suds supressors,softeners, and perfumes. This listing of adjunct cleaning additives isexemplary only, and not by way of limitation of the types of adjunctcleaning additives which can be used. In principle, any adjunct cleaningadditive known in the art may be used in the instant invention.

Polymers

The composition may comprise one or more polymers. Non-limitingexamples, all of which may be optionally modified, includepolyethyleneimines, carboxymethylcellulose, poly(vinyl-pyrrolidone),poly (ethylene glycol), poly(vinyl alcohol),poly(vinylpyridine-N-oxide), poly(vinylimidazole), polycarboxylates oralkoxylated substituted phenols (ASP). as described in WO 2016/041676.An example of ASP dispersants, include but are not limited to, HOSTAPALBV CONC 51000 available from Clariant.

Polyamines may be used for grease, particulate removal or stain removal.A wide variety of amines and polyaklyeneimines can be alkoxylated tovarious degrees to achieve hydrophobic or hydrophilic cleaning. Suchcompounds may include, but are not limited to, ethoxylatedpolyethyleneimine, ethoxylated hexamethylene diamine, and sulfatedversions thereof. Useful examples of such polymers are HP20 availablefrom BASF or a polymer having the following general structure:

bis((C₂HSO)(C₂H₄O)_(n))(CH₃)—N+-C_(x)H_(2x)—N+-(CH₃)-bis((C₂H₅O)(C₂H₄O)_(n)),wherein n=from 20 to 30, and x=from 3 to 8, or sulphated or sulphonatedvariants thereof. Polypropoxylated-polyethoxylated amphiphilicpolyethyleneimine derivatives may also be included to achieve greatergrease removal and emulsification. These may comprise alkoxylatedpolyalkylenimines, preferably having an inner polyethylene oxide blockand an outer polypropylene oxide block. Detergent compositions may alsocontain unmodified polyethyleneimines useful for enhanced beverage stainremoval. PEI's of various molecular weights are commercially availablefrom the BASF Corporation under the trade name Lupasol® Examples ofsuitable PEI's include, but are not limited to, Lupasol FG®, LupasolG-35®.

The composition may comprise one or more carboxylate polymers, such as amaleate/acrylate random copolymer or polyacrylate homopolymer useful aspolymeric dispersing agents. Alkoxylated polycarboxylates such as thoseprepared from polyacrylates are also useful to provide clay dispersancy.Such materials are described in WO 91/08281. Chemically, these materialscomprise polyacrylates having one ethoxy side-chain per every 7-8acrylate units. The side-chains are of the formula —(CH₂CH₂O)_(m)(CH₂)_(n)CH₃ wherein m is 2-3 and n is 6-12. The side-chains are esteror ether-linked to the polyacrylate “backbone” to provide a “comb”polymer type structure.

Preferred amphiphilic graft co-polymer(s) comprise (i) polyethyeleneglycol backbone; and (ii) at least one pendant moiety selected frompolyvinyl acetate, polyvinyl alcohol and mixtures thereof. An example ofan amphiphilic graft co-polymer is Sokalan HP22, supplied from BASF.

Alkoxylated substituted phenols as described in WO 2016/041676 are alsosuitable examples of polymers that provide clay dispersancy. Hostapal BVConc 51000, available from Clariant, is one non-limiting example of anASP dispersant, .

Preferably the composition comprises one or more soil release polymers.Suitable soil release polymers are polyester soil release polymers suchas Repel-o-tex polymers, including Repel-o-tex SF, SF-2 and SRP6supplied by Rhodia. Other suitable soil release polymers include Texcarepolymers, including Texcare SRA100, SRA300, SRN100, SRN170, SRN240,SRN260 SRN300 and SRN325 supplied by Clariant. Other suitable soilrelease polymers are Marloquest polymers, such as Marloquest SL, HSCB,L235M, B, G82 supplied by Sasol. Other suitable soil release polymersinclude methyl-capped ethoxylated propoxylated soil release polymers asdescribed in U.S. Pat. No. 9,365,806.

Preferably the composition comprises one or more polysaccharides whichmay in particular be chosen from carboxymethyl cellulose,methylcarboxymethylcellulose, sulfoethylcellulose,methylhydroxyethylcellulose, carboxymethyl xyloglucan, carboxymethylxylan, sulfoethylgalactomannan, carboxymethyl galactomannan, hydoxyethylgalactomannan, sulfoethyl starch, carboxymethyl starch, and mixturethereof. Other polysaccharides suitable for use in the present inventionare the glucans. Preferred glucans are Poly alpha-1,3-glucan which is apolymer comprising glucose monomeric units linked together by glycosidiclinkages (i.e., glucosidic linkages), wherein at least about 50% of theglycosidic linkages are alpha-1,3-glycosidic linkages. Polyalpha-1,3-glucan is a type of polysaccharide. Poly alpha-1,3-glucan canbe enzymatically produced from sucrose using one or moreglucosyltransferase enzymes, such as described in U.S. Pat. No.7,000,000, and U.S. Patent Appl. Publ. Nos. 2013/0244288 and2013/0244287 (all of which are incorporated herein by reference), forexample.

Other suitable polysaccharides for use in the composition are cationicpolysaccharides. Examples of cationic polysaccharides include cationicguar gum derivatives, quaternary nitrogen-containing cellulose ethers,and synthetic polymers that are copolymers of etherified cellulose, guarand starch. When used, the cationic polymers herein are either solublein the composition or are soluble in a complex coacervate phase in thecomposition formed by the cationic polymer and the anionic, amphotericand/or zwitterionic surfactant component described hereinbefore.Suitable cationic polymers are described in U.S. Pat. Nos. 3,962,418;3,958,581; and U.S. Publication No. 2007/0207109A1.

Polymers can also function as deposition aids for other detergent rawmaterials. Preferred deposition aids are selected from the groupconsisting of cationic and nonionic polymers. Suitable polymers includecationic starches, cationic hydroxyethylcellulose,polyvinylformaldehyde, locust bean gum, mannans, xyloglucans, tamarindgum, polyethyleneterephthalate and polymers containingdimethylaminoethyl methacrylate, optionally with one or more monomersselected from the group comprising acrylic acid and acrylamide.

Additional Amines

Polyamines are known to improve grease removal. Preferred cyclic andlinear amines for performance are 1,3-bis (methylamine)-cyclohexane,4-methylcyclohexane-1,3-diamine (Baxxodur ECX 210 supplied by BASF) 1,3propane diamine, 1,6 hexane diamine,1,3 pentane diamine (Dytek EPsupplied by Invista), 2-methyl 1,5 pentane diamine (Dytek A supplied byInvista). U.S. Pat. No. 6,710,023 discloses hand dishwashingcompositions containing said diamines and polyamines containing at least3 protonable amines. Polyamines according to the invention have at leastone pka above the wash pH and at least two pka's greater than about 6and below the wash pH. Preferred polyamines with are selected from thegroup consisting of tetraethylenepentamine, hexaethylhexamine,heptaethylheptamines, octaethyloctamines, nonethylnonamines, andmixtures thereof commercially available from Dow, BASF and Huntman.Especially preferred polyetheramines are lipophilic modified asdescribed in U.S. Pat. No. 9,752,101, U.S. Pat. No. 9,487,739, U.S. Pat.No. 9,631,163

Dye Transfer Inhibitor (DTI)

The composition may comprise one or more dye transfer inhibiting agents.In one embodiment of the invention the inventors have surprisingly foundthat compositions comprising polymeric dye transfer inhibiting agents inaddition to the specified dye give improved performance. This issurprising because these polymers prevent dye deposition. Suitable dyetransfer inhibitors include, but are not limited to,polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers ofN-vinylpyrrolidone and N-vinylimidazole, polyvinyloxazolidones andpolyvinylimidazoles or mixtures thereof. Suitable examples includePVP-K15, PVP-K30, ChromaBond S-400, ChromaBond S-403E and ChromabondS-100 from Ashland Aqualon, and Sokalan HP165, Sokalan HP50, SokalanHP53, Sokalan HP59, Sokalan® HP 56K, Sokalan® HP 66 from BASF. Othersuitable DTIs are as described in WO2012/004134. When present in asubject composition, the dye transfer inhibiting agents may be presentat levels from about 0.0001% to about 10%, from about 0.01% to about 5%or even from about 0.1% to about 3% by weight of the composition.

Enzymes

Enzymes may be included in the cleaning compositions for a variety ofpurposes, including removal of protein-based, carbohydrate-based, ortriglyceride-based stains from substrates, for the prevention of refugeedye transfer in fabric laundering, and for fabric restoration. Suitableenzymes include proteases, amylases, lipases, carbohydrases, cellulases,oxidases, peroxidases, mannanases, and mixtures thereof of any suitableorigin, such as vegetable, animal, bacterial, fungal, and yeast origin.Other enzymes that may be used in the cleaning compositions describedherein include hemicellulases, peroxidases, proteases, cellulases,endoglucanases, xylanases, lipases, phospholipases, amylases,gluco-amylases, xylanases, esterases, cutinases, pectinases,keratanases, reductases, oxidases, phenoloxidases, lipoxygenases,ligninases, pullulanases, tannases, pentosanases, malanases,β-glucanases, arabinosidases, hyaluronidases, chondroitinases, laccases,or mixtures thereof, esterases, mannanases, pectate lyases, and ormixtures thereof. Other suitable enzymes include Nuclease enzyme. Thecomposition may comprise a nuclease enzyme. The nuclease enzyme is anenzyme capable of cleaving the phosphodiester bonds between thenucleotide sub-units of nucleic acids. The nuclease enzyme herein ispreferably a deoxyribonuclease or ribonuclease enzyme or a functionalfragment thereof. Enzyme selection is influenced by factors such aspH-activity and/or stability optima, thermostability, and stability toactive detergents, builders, and the like.

The enzymes may be incorporated into the cleaning composition at levelsfrom 0.0001% to 5% of active enzyme by weight of the cleaningcomposition. The enzymes can be added as a separate single ingredient oras mixtures of two or more enzymes.

In some embodiments, lipase may be used. Lipase may be purchased underthe trade name Lipex from Novozymes (Denmark). Amylases (Natalase®,Stainzyme®, Stainzyme Plus®) may be supplied by Novozymes, Bagsvaerd,Denmark. Proteases may be supplied by Genencor International, Palo Alto,Calif., USA (e.g. Purafect Prime®) or by Novozymes, Bagsvaerd, Denmark(e.g. Liquanase®, Coronase®, Savinase®. Other preferred enzymes includepectate lyases preferably those sold under the trade names Pectawash®,Xpect®, Pectaway® and the mannanases sold under the trade namesMannaway® (all from Novozymes A/S, Bagsvaerd, Denmark), and Purabrite®(Genencor International Inc., Palo Alto, Calif.). A range of enzymematerials and means for their incorporation into synthetic cleaningcompositions is disclosed in WO 9307263 A; WO 9307260 A; WO 8908694 A;U.S. Pat. Nos. 3,553,139; 4,101,457; and U.S. Pat. No. 4,507,219. Enzymematerials useful for liquid cleaning compositions, and theirincorporation into such compositions, are disclosed in U.S. Pat. No.4,261,868.

Enzyme Stabilizing System

The enzyme-containing compositions described herein may optionallycomprise from about 0.001% to about 10%, in some examples from about0.005% to about 8%, and in other examples, from about 0.01% to about 6%,by weight of the composition, of an enzyme stabilizing system. Theenzyme stabilizing system can be any stabilizing system which iscompatible with the detersive enzyme. Such a system may be inherentlyprovided by other formulation actives, or be added separately, e.g., bythe formulator or by a manufacturer of detergent-ready enzymes. Suchstabilizing systems can, for example, comprise calcium ion, boric acid,propylene glycol, short chain carboxylic acids, boronic acids, chlorinebleach scavengers and mixtures thereof, and are designed to addressdifferent stabilization problems depending on the type and physical formof the cleaning composition. See U.S. Pat. No. 4,537,706 for a review ofborate stabilizers.

Chelating Agent.

Preferably the composition comprises chelating agents and/or crystalgrowth inhibitor. Suitable molecules include copper, iron and/ormanganese chelating agents and mixtures thereof. Suitable moleculesinclude aminocarboxylates, aminophosphonates, succinates, salts thereof,and mixtures thereof. Non-limiting examples of suitable chelants for useherein include ethylenediaminetetracetates,N-(hydroxyethyl)-ethylene-diamine-triacetates, nitrilotriacetates,ethylenediamine tetraproprionates, triethylene-tetraamine-hexacetates,diethylenetriamine-pentaacetates, ethanoldiglycines,ethylenediaminetetrakis (methylenephosphonates), diethylenetriaminepenta(methylene phosphonic acid) (DTPMP), ethylenediamine disuccinate(EDDS), hydroxyethanedimethylenephosphonic acid (HEDP),methylglycinediacetic acid (MGDA), diethylenetriaminepentaacetic acid(DTPA), and 1,2-diydroxybenzene-3,5-disulfonic acid (Tiron), saltsthereof, and mixtures thereof. Tiron as well as other sulphonatedcatechols may also be used as effective heavy metal chelants. Othernon-limiting examples of chelants of use in the present invention arefound in U.S. Pat. Nos. 7,445,644, 7,585,376 and 2009/0176684A1. Othersuitable chelating agents for use herein are the commercial DEQUESTseries, and chelants from Monsanto, DuPont, and Nalco Inc.

Brighteners

Optical brighteners or other brightening or whitening agents may beincorporated at levels of from about 0.01% to about 1.2%, by weight ofthe composition, into the cleaning compositions described herein.Commercial optical brighteners, which may be used herein, can beclassified into subgroups, which include, but are not necessarilylimited to, derivatives of stilbene, pyrazoline, coumarin, carboxylicacid, methinecyanines, dibenzothiphene-5,5-dioxide, azoles, S- and6-membered-ring heterocycles, and other miscellaneous agents. Examplesof such brighteners are disclosed in “The Production and Application ofFluorescent Brightening Agents,” M. Zahradnik, John Wiley & Sons, NewYork (1982). Specific, non-limiting examples of optical brightenerswhich may be useful in the present compositions are those identified inU.S. Pat. No. 4,790,856 and U.S. Pat. No. 3,646,015. Highly preferredBrighteners include Disodium4,4′-bis{[4-anilino-6-[bis(2-hydroxyethyl)amino-s-triazin-2-yl]-amino}-2,2′-stilbenedisulfonate,4,4′-bis{[4-anilino-6-morpholino-s-triazin-2-yl]-amino}-2,2′-stilbenedisulfonate,Disodium4,4″-bis[(4,6-di-anilino-s-triazin-2-yl)-amino]-2,2′-stilbenedisulfonateand disodium 4,4′-bis-(2-sulfostyryl)biphenyl.

Bleaching Agents.

It may be preferred for the composition to comprise one or morebleaching agents. Suitable bleaching agents include photobleaches,hydrogen peroxide, sources of hydrogen peroxide, pre-formed peracids andmixtures thereof.

(1) photobleaches for example sulfonated zinc phthalocyanine sulfonatedaluminium phthalocyanines, xanthene dyes and mixtures thereof;

(2) pre-formed peracids: Suitable preformed peracids include, but arenot limited to compounds selected from the group consisting ofpre-formed peroxyacids or salts thereof typically a percarboxylic acidsand salts, percarbonic acids and salts, perimidic acids and salts,peroxymonosulfuric acids and salts, for example, Oxone®, and mixturesthereof. Suitable examples include peroxycarboxylic acids or saltsthereof, or peroxysulphonic acids or salts thereof. Particularlypreferred peroxyacids are phthalimido-peroxy-alkanoic acids, inparticular ε-phthalimido peroxy hexanoic acid (PAP). Preferably, theperoxyacid or salt thereof has a melting point in the range of from 30oC to 60 oC.

(3) sources of hydrogen peroxide, for example, inorganic perhydratesalts, including alkali metal salts such as sodium salts of perborate(usually mono- or tetra-hydrate), percarbonate, persulphate,perphosphate, persilicate salts and mixtures thereof.

Fabric Shading Dyes

The fabric shading dye (sometimes referred to as hueing, bluing orwhitening agents) typically provides a blue or violet shade to fabric.Such dye(s) are well known in the art and may be used either alone or incombination to create a specific shade of hueing and/or to shadedifferent fabric types. The fabric shading dye may be selected from anychemical class of dye as known in the art, including but not limited toacridine, anthraquinone (including polycyclic quinones), azine, azo(e.g., monoazo, disazo, trisazo, tetrakisazo, polyazo), benzodifurane,benzodifuranone, carotenoid, coumarin, cyanine, diazahemicyanine,diphenylmethane, formazan, hemicyanine, indigoids, methane,naphthalimides, naphthoquinone, nitro, nitroso, oxazine, phthalocyanine,pyrazoles, stilbene, styryl, triarylmethane, triphenylmethane, xanthenesand mixtures thereof. The amount of adjunct fabric shading dye presentin a laundry care composition of the invention is typically from 0.0001to 0.05 wt % based on the total cleaning composition, preferably from0.0001 to 0.005 wt %. Based on the wash liquor, the concentration offabric shading dye typically is from 1 ppb to 5 ppm, preferably from 10ppb to 500 ppb.

Suitable fabric shading dyes include small molecule dyes, polymeric dyesand dye-clay conjugates. Preferred fabric shading dyes are selected fromsmall molecule dyes and polymeric dyes. Suitable small molecule dyes maybe selected from the group consisting of dyes falling into the ColourIndex (C. I., Society of Dyers and Colourists, Bradford, UK)classifications of Acid, Direct, Basic, Reactive, Solvent or Dispersedyes.

Suitable polymeric dyes include dyes selected from the group consistingof polymers containing covalently bound (sometimes referred to asconjugated) chromogens, (also known as dye-polymer conjugates), forexample polymers with chromogen monomers co-polymerized into thebackbone of the polymer and mixtures thereof. Preferred polymeric dyescomprise the optionally substituted alkoxylated dyes, such asalkoxylated triphenyl-methane polymeric colourants, alkoxylatedcarbocyclic and alkoxylated heterocyclic azo colourants includingalkoxylated thiophene polymeric colourants, and mixtures thereof, suchas the fabric-substantive colorants sold under the name of Liquitint®(Milliken, Spartanburg, S.C., USA).

Suitable dye clay conjugates include dye clay conjugates selected fromthe group comprising at least one cationic/basic dye and a smectiteclay; a preferred clay may be selected from the group consisting ofMontmorillonite clay, Hectorite clay, Saponite clay and mixturesthereof.

Pigments are well known in the art and may also be used in the laundrycare compositions herein. Suitable pigments include C. I Pigment Blues15 to 20, especially 15 and/or 16, C. I. Pigment Blue 29, C. I. PigmentViolet 15, Monastral Blue and mixtures thereof.

Builders

The cleaning compositions of the present invention may optionallycomprise a builder. Builders selected from aluminosilicates andsilicates assist in controlling mineral hardness in wash water, or toassist in the removal of particulate soils from surfaces. Suitablebuilders may be selected from the group consisting of phosphatespolyphosphates, especially sodium salts thereof; carbonates,bicarbonates, sesquicarbonates, and carbonate minerals other than sodiumcarbonate or sesquicarbonate; organic mono-, di-, tri-, andtetracarboxylates, especially water-soluble non-surfactant carboxylatesin acid, sodium, potassium or alkanolammonium salt form, as well asoligomeric or water-soluble low molecular weight polymer carboxylatesincluding aliphatic and aromatic types; and phytic acid. These may becomplemented by borates, e.g., for pH-buffering purposes, or bysulfates, especially sodium sulfate and any other fillers or carrierswhich may be important to the engineering of stable surfactant and/orbuilder-containing cleaning compositions.

pH Buffer System

The compositions may also include a pH buffer system. The cleaningcompositions herein may be formulated such that, during use in aqueouscleaning operations, the wash water will have a pH of between about 6.0and about 12, and in some examples, between about 7.0 and 11. Techniquesfor controlling pH at recommended usage levels include the use ofbuffers, alkalis, or acids, and are well known to those skilled in theart. These include, but are not limited to, the use of sodium carbonate,citric acid or sodium citrate, monoethanol amine or other amines, boricacid or borates, and other pH-adjusting compounds well known in the art.The cleaning compositions herein may comprise dynamic in-wash pHprofiles by delaying the release of citric acid.

Structurant/Thickeners

Structured liquids can either be internally structured, whereby thestructure is formed by primary ingredients (e.g. surfactant material)and/or externally structured by providing a three dimensional matrixstructure using secondary ingredients (e.g. polymers, clay and/orsilicate material). The composition may comprise from about 0.01% toabout 5%, by weight of the composition, of a structurant, and in someexamples, from about 0.1% to about 2.0%, by weight of the composition,of a structurant. The structurant may be selected from the groupconsisting of diglycerides and triglycerides, ethylene glycoldistearate, microcrystalline cellulose, cellulose-based materials,microfiber cellulose, biopolymers, xanthan gum, gellan gum, and mixturesthereof. In some examples, a suitable structurant includes hydrogenatedcastor oil, and non-ethoxylated derivatives thereof. Other suitablestructurants are disclosed in U.S. Pat. No. 6,855,680. Such structurantshave a thread-like structuring system having a range of aspect ratios.Further suitable structurants and the processes for making them aredescribed in WO 2010/034736.

Suds Suppressors

Compounds for reducing or suppressing the formation of suds can beincorporated into the cleaning compositions described herein. Sudssuppression can be of particular importance in the so-called “highconcentration cleaning process” as described in U.S. Pat. Nos.4,489,455, 4,489,574, and in front-loading style washing machines.

A wide variety of materials may be used as suds suppressors, and sudssuppressors are well known to those skilled in the art. See, forexample, Kirk Othmer Encyclopedia of Chemical Technology, Third Edition,Volume 7, pages 430-447 (John Wiley & Sons, Inc., 1979). Examples ofsuds suppressors include monocarboxylic fatty acid, and soluble saltstherein, high molecular weight hydrocarbons such as paraffin, fatty acidesters (e.g., fatty acid triglycerides), fatty acid esters of monovalentalcohols, aliphatic C18-C40 ketones (e.g., stearone), N-alkylated aminotriazines, waxy hydrocarbons preferably having a melting point belowabout 100° C., silicone suds suppressors, and secondary alcohols. Sudssuppressors are described in U.S. Pat. Nos. 2,954,347; 4,075,118;4,265,779; 4,265,779; 3,455,839; 3,933,672; 4,652,392; 4,978,471;4,983,316; 5,288,431; 4,639,489; 4,749,740; and 4,798,679.

The cleaning compositions herein may comprise from 0% to about 10%, byweight of the composition, of suds suppressor. When utilized as sudssuppressors, monocarboxylic fatty acids, and salts thereof, may bepresent in amounts up to about 5% by weight of the cleaning composition,and in some examples, may be from about 0.5% to about 3% by weight ofthe cleaning composition. Silicone suds suppressors may be utilized inamounts up to about 2.0% by weight of the cleaning composition, althoughhigher amounts may be used. Monostearyl phosphate suds suppressors maybe utilized in amounts ranging from about 0.1% to about 2% by weight ofthe cleaning composition. Hydrocarbon suds suppressors may be utilizedin amounts ranging from about 0.01% to about 5.0% by weight of thecleaning composition, although higher levels can be used. Alcohol sudssuppressors may be used at about 0.2% to about 3% by weight of thecleaning composition.

Suds Boosters

If high sudsing is desired, suds boosters such as the C10-C16alkanolamides may be incorporated into the cleaning compositions fromabout 1% to about 10% by weight of the cleaning composition. Someexamples include the C10-C14 monoethanol and diethanol amides. Ifdesired, water-soluble magnesium and/or calcium salts such as MgCl₂,MgSO₄, CaCl₂, CaSO₄, and the like, may be added at levels of about 0.1%to about 2% by weight of the cleaning composition, to provide additionalsuds and to enhance grease removal performance.

Fillers and Carriers

Fillers and carriers may be used in the cleaning compositions describedherein. As used herein, the terms “filler” and “carrier” have the samemeaning and can be used interchangeably.

Liquid cleaning compositions, and other forms of cleaning compositionsthat include a liquid component (such as liquid-containing unit dosecleaning compositions), may contain water and other solvents as fillersor carriers. Low molecular weight primary or secondary alcoholsexemplified by methanol, ethanol, propanol, isopropanol, andphenoxyethanol are suitable. Monohydric alcohols may be used in someexamples for solubilizing surfactants, and polyols such as thosecontaining from 2 to about 6 carbon atoms and from 2 to about 6 hydroxygroups (e.g., 1,2-propanediol, 1,3-propanediol, 2,3-butanediol, ethyleneglycol, and glycerine may be used). Amine-containing solvents may alsobe used.

Methods of Use

The present invention includes methods for whitening fabric. Compactfluid detergent compositions that are suitable for sale to consumers aresuited for use in laundry pretreatment applications, laundry cleaningapplications, and home care applications. Such methods include, but arenot limited to, the steps of contacting detergent compositions in neatform or diluted in wash liquor, with at least a portion of a fabricwhich may or may not be soiled and then optionally rinsing the fabric.The fabric material may be subjected to a washing step prior to theoptional rinsing step. Machine laundry methods may comprise treatingsoiled laundry with an aqueous wash solution in a washing machine havingdissolved or dispensed therein an effective amount of a machine laundrydetergent composition in accord with the invention. An “effectiveamount” of the detergent composition means from about 20 g to about 300g of product dissolved or dispersed in a wash solution of volume fromabout 5 L to about 65 L. The water temperatures may range from about 5°C. to about 100° C. The water to soiled material (e.g., fabric) ratiomay be from about 1:1 to about 30:1. The compositions may be employed atconcentrations of from about 500 ppm to about 15,000 ppm in solution. Inthe context of a fabric laundry composition, usage levels may also varydepending not only on the type and severity of the soils and stains, butalso on the wash water temperature, the volume of wash water, and thetype of washing machine (e.g., top-loading, front-loading, vertical-axisJapanese-type automatic washing machine).

The detergent compositions herein may be used for laundering of fabricsat reduced wash temperatures. These methods of laundering fabriccomprise the steps of delivering a laundry detergent composition towater to form a wash liquor and adding a laundering fabric to said washliquor, wherein the wash liquor has a temperature of from about 0° C. toabout 20° C., or from about 0° C. to about 15° C., or from about 0° C.to about 9° C. The fabric may be contacted to the water prior to, orafter, or simultaneous with, contacting the laundry detergentcomposition with water. Another method includes contacting a nonwovensubstrate, which is impregnated with the detergent composition, with asoiled material. As used herein, “nonwoven substrate” can comprise anyconventionally fashioned nonwoven sheet or web having suitable basisweight, caliper (thickness), absorbency, and strength characteristics.Non-limiting examples of suitable commercially available nonwovensubstrates include those marketed under the trade names SONTARA® byDuPont and POLY WEB® by James River Corp.

Hand washing/soak methods, and combined hand washing with semi-automaticwashing machines, are also included.

Packaging for the Compositions

The cleaning compositions described herein can be packaged in anysuitable container including those constructed from paper, cardboard,plastic materials, and any suitable laminates. An optional packagingtype is described in European Application No. 94921505.7.

Multi-Compartment Pouch

The cleaning compositions described herein may also be packaged as amulti-compartment cleaning composition.

Other Adjunct Ingredients

A wide variety of other ingredients may be used in the cleaningcompositions herein, including, for example, other active ingredients,carriers, hydrotropes, processing aids, dyes or pigments, solvents forliquid formulations, solid or other liquid fillers, erythrosine,colliodal silica, waxes, probiotics, surfactin, aminocellulosicpolymers, Zinc Ricinoleate, perfume microcapsules, rhamnolipds,sophorolipids, glycopeptides, methyl ester ethoxylates, sulfonatedestolides, cleavable surfactants, biopolymers, silicones, modifiedsilicones, aminosilicones, deposition aids, hydrotropes (especiallycumene-sulfonate salts, toluene-sulfonate salts, xylene-sulfonate salts,and naphalene salts), PVA particle-encapsulated dyes or perfumes,pearlescent agents, effervescent agents, color change systems, siliconepolyurethanes, opacifiers, tablet disintegrants, biomass fillers,fast-dry silicones, glycol distearate, starch perfume encapsulates,emulsified oils including hydrocarbon oils, polyolefins, and fattyesters, bisphenol antioxidants, micro-fibrous cellulose structurants,properfumes, styrene/acrylate polymers, triazines, soaps, superoxidedismutase, benzophenone protease inhibitors, functionalized TiO2,dibutyl phosphate, silica perfume capsules, and other adjunctingredients, choline oxidase, triarylmethane blue and violet basic dyes,methine blue and violet basic dyes, anthraquinone blue and violet basicdyes, azo dyes basic blue 16, basic blue 65, basic blue 66 basic blue67, basic blue 71, basic blue 159, basic violet 19, basic violet 35,basic violet 38, basic violet 48, oxazine dyes, basic blue 3, basic blue75, basic blue 95, basic blue 122, basic blue 124, basic blue 141, Nileblue A and xanthene dye basic violet 10, an alkoxylated triphenylmethanepolymeric colorant; an alkoxylated thiopene polymeric colorant;thiazolium dye, mica, titanium dioxide coated mica, bismuth oxychloride,and other actives.

Anti-oxidant: The composition may optionally contain an anti-oxidantpresent in the composition from about 0.001 to about 2% by weight.Preferably the antioxidant is present at a concentration in the range0.01 to 0.08% by weight. Mixtures of anti-oxidants may be used.

One class of anti-oxidants used in the present invention is alkylatedphenols. Hindered phenolic compounds are a preferred type of alkylatedphenols having this formula. A preferred hindered phenolic compound ofthis type is 3,5-di-tert-butyl-4-hydroxytoluene (BHT).

Furthermore, the anti-oxidant used in the composition may be selectedfrom the group consisting of α-, β-, γ-, δ-tocopherol, ethoxyquin,2,2,4-trimethyl-1,2-dihydroquinoline, 2,6-di-tert-butyl hydroquinone,tert-butyl hydroxyanisole, lignosulphonic acid and salts thereof, andmixtures thereof.

The cleaning compositions described herein may also contain vitamins andamino acids such as: water soluble vitamins and their derivatives, watersoluble amino acids and their salts and/or derivatives, water insolubleamino acids viscosity modifiers, dyes, nonvolatile solvents or diluents(water soluble and insoluble), pearlescent aids, pediculocides, pHadjusting agents, preservatives, skin active agents, sunscreens, UVabsorbers, niacinamide, caffeine, and minoxidil.

The cleaning compositions of the present invention may also containpigment materials such as nitroso, monoazo, disazo, carotenoid,triphenyl methane, triaryl methane, xanthene, quinoline, oxazine, azine,anthraquinone, indigoid, thionindigoid, quinacridone, phthalocianine,botanical, and natural colors, including water soluble components suchas those having C. I. Names.

The cleaning compositions of the present invention may also containantimicrobial agents. Cationic active ingredients may include but arenot limited to n-alkyl dimethyl benzyl ammonium chloride, alkyl dimethylethyl benzyl ammonium chloride, dialkyl dimethyl quaternary ammoniumcompounds such as didecyl dimethyl ammonium chloride,N,N-didecyl-Nmethyl-poly(oxyethyl) ammonium propionate, dioctyl didecylammonium chloride, also including quaternary species such asbenzethonium chloride and quaternary ammonium compounds with inorganicor organic counter ions such as bromine, carbonate or other moietiesincluding dialkyl dimethyl ammonium carbonates, as well as antimicrobialamines such as Chlorhexidine Gluconate, PHMB (Polyhexamethylenebiguanide), salt of a biguanide, a substituted biguanide derivative, anorganic salt of a quaternary ammonium containing compound or aninorganic salt of a quaternary ammonium containing compound or mixturesthereof.

In one aspect, such method comprises the steps of optionally washingand/or rinsing said surface or fabric, contacting said surface or fabricwith any composition disclosed in this specification then optionallywashing and/or rinsing said surface or fabric is disclosed, with anoptional drying step.

Drying of such surfaces or fabrics may be accomplished by any one of thecommon means employed either in domestic or industrial settings. Thefabric may comprise any fabric capable of being laundered in normalconsumer or institutional use conditions, and the invention is suitablefor cellulosic substrates and in some aspects also suitable forsynthetic textiles such as polyester and nylon and for treatment ofmixed fabrics and/or fibers comprising synthetic and cellulosic fabricsand/or fibers. As examples of synthetic fabrics are polyester, nylon,these may be present in mixtures with cellulosic fibers, for example,polycotton fabrics. The solution typically has a pH of from 7 to 11,more usually 8 to 10.5. The compositions are typically employed atconcentrations from 500 ppm to 5,000 ppm in solution. The watertemperatures typically range from about 5° C. to about 90° C. The waterto fabric ratio is typically from about 1:1 to about 30:1.

In a further embodiment, the invention provides a domestic method oftreating a textile material, the method comprising the steps of (a)treating the textile material with an aqueous solution of the leucopolymer, (b) optionally, rinsing the textile material, and (c)optionally, drying the textile material.

The leuco polymer used in the domestic treatment method can be any ofthe leuco polymers described above in connection with the earlierembodiments of the invention. The leuco polymer can be present in theaqueous solution in any suitable amount. In one aspect, the aqueoussolution comprises from about 10 ppb to about 5,000 ppm, preferablyabout 50 ppb to about 2 ppm, of the leuco polymer. In such anembodiment, the aqueous solution can further comprise a surfactant in anamount of from 0.0 g/L to about 6 g/L, preferably about 0.2 g/L to about4 g/L. Further, the aqueous solution utilized in the domestic treatmentmethod can be prepared by combining any of the laundry care compositionsdescribed above with a suitable amount of water. The domestic treatmentmethod can be performed in any suitable apparatus, such as a sink or adomestic clothes washing machine.

The following examples further illustrate the subject matter describedabove but, of course, should not be construed as in any way limiting thescope thereof.

EXAMPLES

Preparation of alkoxylated polyethylene imine:

122.2 gram of the unsubstituted initial polyethylenimine (PEI1)containing (2×9)+(1×13)=31 amine hydrogens on the primary and secondarynitrogen atoms is charged to a pressure reactor. Then 150.1 g propyleneoxide (2.6 mol, 83.9 mol. % of the amine hydrogens of the primary andsecondary nitrogen atoms) is added to the reactor. The reaction isagitated at 120° C. under pressure until the pressure stabilizes (˜8hours). The product (PEI 2) is obtained with 83.9 mol % of aminehydrogens replaced by a 2-hydroxypropyl group or a 1-hydroxypropane-2-ylgroup. In the structure below, only 2-hydroxypropyl groups have beenshown for the sake of simplicity.

Preparation of alkoxylated polyethylene imine with alkene chain.

To 273 gram (0.1 mol) of the PEI 2 obtained above, 28.4 gram (0. 1 mol,equilibrate 3.2% of the amino hydrogen to PEI 1) is added. The reactionmixture is stirred to 180° C. for 16 hours under nitrogen to obtainPEI4.

Preparation of Leuco Monomers

Leuco alcohol 3: A solution of 4,4′-bis(dimethylamino)benzhydrol (1)(0.27 g, 1.0 mmol), 2-(methylphenylamino)ethanol (2) (0.18 g, 1.2 mmol),and p-toluenesulfonic acid (pTSA) monohydrate (0.76 g, 4 mmol) inmethanol (25 mL) is stirred at reflux with a Dean-Stark trap for 9 h.The mixture is diluted with methylene chloride and washed three timeswith aq. sodium bicarbonate. The organic layer is dried over anhydrousMgSO₄ and filtered. The filtrate is concentrated in vacuo to give aresidue which is purified by column chromatography on silica gel (1:1ethyl acetate/hexane) to yield the leuco alcohol intermediate 3.

Preparation of Leuco Tosylate

Leuco tosylate 4: A solution of leuco alcohol (3) (5 g, 12.4 mmol),p-toluene sulfonyl chloride (2.6 g, 13.5 mmol), and a catalytic amountof pyridine (0.2 mL) in acetonitrile (50 mL) is refluxed for 12 h. Themixture is diluted with methylene chloride and washed three times withaq. sodium bicarbonate. The organic layer is dried over anhydrous Na₂SO₄and filtered. The filtrate is concentrated in vacuo to give a residuewhich is purified by column chromatography on silica gel (1:1 ethylacetate/hexane) to yield the leuco tosylate intermediate 4.

Preparation of Leuco Polymer 5

Leuco Polymer 5: A solution of PEI4 (5.42 g, 1.8 mmol) and Leucotosylate 4 (1 g, 1.8 mmol) in dichloroethane (20 mL) is heated at 65° C.for 12 h. The reaction is monitored using thin layer chromatography.Excess dichloroethane is evaporated by rotary evaporation to obtain theleuco polymer 5.

Test Methods

Fabric swatches used in the test methods herein are obtained fromTestfabrics, Inc. West Pittston, PA, and are 100% Cotton, Style 403 (cutto 2″×2″) and/or Style 464 (cut to 4″×6″), and an unbrightenedmultifiber fabric, specifically Style 41 (5 cm×10 cm).

All reflectance spectra and color measurements, including L*, a*, b*,K/S, and Whiteness Index (WI CIE) values on dry fabric swatches, aremade using one of four spectrophotometers: (1) a Konica-Minolta 3610dreflectance spectrophotometer (Konica Minolta Sensing Americas, Inc.,Ramsey, N.J., USA; D65 illumination, 10° observer, UV light excluded),(2) a LabScan XE reflectance spectrophotometer (HunterLabs, Reston, Va.;D65 illumination, 10° observer, UV light excluded), (3) a Color-Eye®7000A (GretagMacbeth, New Windsor, N.Y., USA; D65 light, UV excluded),or (4) a Color i7 spectrophotometer (X-rite, Inc., Grand Rapids, Mich.,USA; D65 light, UV excluded). Measurements are performed using twolayers of fabric, obtained by stacking smaller internal replicates(e.g., 2″×2″ Style 403) or folding of larger fabric swatches (e.g.,4″×6″ style 464).

Where fabrics are irradiated, unless otherwise indicated, the specifiedfabrics post-dry are exposed to simulated sunlight with irradiance of0.77 W/m²@420 nm in an Atlas Xenon Fade-Ometer Ci3000+ (Atlas MaterialTesting Technology, Mount Prospect, Ill., USA) equipped with Type SBorosilicate inner (Part no. 20277300) and outer (Part no. 20279600)filters, set at 37° C. maximum cabinet temperature, 57° C. maximum blackpanel temperature (BPT black panel geometry), and 35% RH (relativehumidity). Unless otherwise indicated, irradiation is continuous overthe stated duration.

I. Method for Determining Leuco Compound Efficiency from a Wash Solution

Cotton swatches (Style 403) are stripped prior to use by washing at 49°C. two times with heavy duty liquid laundry detergent nil brightener(1.55 g/L in aqueous solution). A concentrated stock solution of eachleuco polymer to be tested is prepared in a solvent selected fromethanol or 50:50 ethanol:water, preferably ethanol.

A base wash solution is prepared by dissolving heavy duty liquid laundrydetergent nil brightener (5.23 g/1.0 L) in deionized water. Fourstripped cotton swatches are weighed together and placed in a 250 mLErlenmeyer flask along with two 10 mm glass marbles. A total of threesuch flasks are prepared for each wash solution to be tested. The basewash solution is dosed with the leuco polymer stock to achieve a washsolution with the desired 2.0×10⁻⁶ N wash concentration of leucomoieties. (By way of example, a 1.0 ppm wash solution of a leuco polymerwith equivalent weight of 493.65 g/equivalent leuco moiety, or a 1.5 ppmwash solution of a leuco colorant with equivalent weight of 757.97g/equivalent leuco moiety, provides a wash solution that is 2.0×10⁻⁶ Nin leuco moeity.)

An aliquot of this wash solution sufficient to provide a 10.0:1.0liquor:fabric (w/w) ratio is placed into each of the three 250 mLErlenmeyer flasks. Each flask is dosed with a 1000 gpg stock hardnesssolution to achieve a final wash hardness of 6 gpg (3:1 Ca:Mg).

The flasks are placed on a Model 75 wrist action shaker (BurrellScientific, Inc., Pittsburg, Pa.) and agitated at the maximum settingfor 12 minutes, after which the wash solution is removed by aspiration,a volume of rinse water (0 gpg) equivalent to the amount of washsolution used is added. Each flask is dosed with a 1000 gpg stockhardness solution to achieve a final rinse hardness of 6 gpg (3:1 Ca:Mg)before agitating 4 more minutes. The rinse is removed by aspiration andthe fabric swatches are spun dry (Mini Countertop Spin Dryer, TheLaundry Alternative Inc., Nashua, N.H.) for 1 minute, then placed in afood dehydrator set at 135° F. to dry in the dark for 2 hours.

A. Dark Conditions Post-Dry

L*, a*, b*, and Whiteness Index (WI CIE) values for the cotton fabricsare measured on the dry swatches 48 hours following the drying procedureusing a LabScan XE reflectance spectrophotometer. The L*, a*, and b*values of the 12 swatches generated for each leuco compound (threeflasks with four swatches each) are averaged and the leuco compoundefficiency (LCE) of each leuco compound is calculated using thefollowing equation:

LCE=DE*=[(L* _(c) −L* _(s))²+(a* _(c) −a* _(s))²+(b* _(c) −b*_(s))²]^(1/2)

wherein the subscripts c and s respectively refer to the control, i.e.,the fabric washed in detergent with no leuco polymer, and the sample,i.e., the fabric washed in detergent containing leuco polymer.

The WI CIE values of the 12 swatches generated for each wash solution(three flasks with four swatches each) are averaged and the change inwhiteness index on washing is calculated using the following equation:

ΔWI=WI CIE (after wash)−WI CIE (before wash)

B. Light conditions post-dry

Because consumer habits vary greatly throughout the world, the methodsused must allow for the possibility of measuring the benefits of leucocompounds across conditions. One such condition is the exposure to lightfollowing drying. Some leuco compounds will not exhibit as large abenefit under dark storage as under light storage, so each leucocompound must be tested under both sets of conditions to determine theoptimum benefit. Therefore Method I includes exposure of the driedfabrics to simulated sunlight for various increments of time beforemeasurements are taken, and the LCE value is set to the maximum valueobtained from the set of exposure times described below.

The specified cotton fabrics post-dry are exposed to simulated sunlightfor 15 min, 30 min, 45 min, 60 min, 75 min, 90 min, 120 min, and 240min. The L*, a*, b*, and Whiteness Index (WI CIE) values for the cottonfabrics are measured on the swatches after each exposure period using aLabScan XE reflectance spectrophotometer. The calculation of the LCE andthe OWI value at each exposure time point is as described in Method I.A.above, and the LCE value and the OWI value for the leuco compound areset to the maximum values obtained from the set of exposure timeslisted.

II. Method for Determining Relative Hue Angle (vs. Nil Leuco Compound)

The relative hue angle delivered by a leuco compound to cotton fabricstreated according to Method I described above is determined as follows.

-   -   a) The a* and b* values of the 12 swatches from each solution        are averaged and the following formulas used to determine Δa*        and Δb*:

Δa*=a* _(s) −a* _(c a) and Δb*=b* _(s) −b* _(c)

-   -   wherein the subscripts c and s respectively refer to the fabric        washed in detergent with no leuco compound and the fabric washed        in detergent containing leuco compound.    -   b) If the absolute value of both Δa* and Δb*<0.25, no Relative        Hue Angle (RHA) is calculated. If the absolute value of either        Δa* or Δb* is ≥0.25, the RHA is determined using one of the        following formulas:

RHA=ATAN2(Δa*,Δb*) for Δb*≥0

RHA=360+ATAN2(Δa*,Δb*) for Δb*<0

A relative hue angle can be calculated for each time point where data iscollected in either the dark post-dry or light post-dry assessments. Anyof these points may be used to satisfy the requirements of a claim.

III. Method for Determining Change in Whiteness Index for a Laundry CareFormulation

Cotton swatches (Style 403) are stripped prior to use by washing at 49°C. two times with heavy duty liquid laundry detergent nil brightener(1.55 g/L in aqueous solution).

A base wash solution is prepared by dissolving the laundry careformulation (5.23 g/1.0 L) in deionized water. Four stripped cottonswatches are weighed together and placed in a 250 mL Erlenmeyer flaskalong with two 10 mm glass marbles. A total of three such flasks areprepared.

An aliquot of this wash solution sufficient to provide a 10.0:1.0liquor:fabric (w/w) ratio is placed into each of the three 250 mLErlenmeyer flasks. Each flask is dosed with a 1000 gpg stock hardnesssolution to achieve a final wash hardness of 6 gpg (3:1 Ca:Mg).

The flasks are placed on a Model 75 wrist action shaker (BurrellScientific, Inc., Pittsburg, PA) and agitated at the maximum setting for12 minutes, after which the wash solution is removed by aspiration, avolume of rinse water (0 gpg) equivalent to the amount of wash solutionused is added. Each flask is dosed with a 1000 gpg stock hardnesssolution to achieve a final rinse hardness of 6 gpg (3:1 Ca:Mg) beforeagitating 4 more minutes. The rinse is removed by aspiration and thefabric swatches are spun dry (Mini Countertop Spin Dryer, The LaundryAlternative Inc., Nashua, N.H.) for 1 minute, then placed in a fooddehydrator set at 135° F. to dry in the dark for 2 hours.

L*, a*, b*, and Whiteness Index (WI CIE) values for the cotton fabricsare measured on the dry swatches, according to Method I.A. and/or I.B.above, using a LabScan XE reflectance spectrophotometer. The WI CIEvalues of the 12 swatches generated for the laundry care formulation(three flasks with four swatches each) are averaged and the change inwhiteness index on washing is calculated using the following equation:

ΔWI=WI CIE (after wash)−WI CIE (before wash)

FORMULATION EXAMPLES

The following are illustrative examples of cleaning compositionsaccording to the present disclosure and are not intended to be limiting.

Examples 1-7 Heavy Duty Liquid Laundry Detergent Compositions

1 2 3 4 5 6 7 Ingredients % weight AE_(1.8)S 6.77 5.16 1.36 1.30 — — —AE₃S — — — — 0.45 — — LAS 0.86 2.06 2.72 0.68 0.95 1.56 3.55 HSAS 1.852.63 1.02 — — — — AE9 6.32 9.85 10.20  7.92 AE8 35.45  AE7 8.40 12.44 C₁₂₋₁₄ dimethyl Amine Oxide 0.30 0.73 0.23 0.37 — — — C₁₂₋₁₈ Fatty Acid0.80 1.90 0.60 0.99 1.20 — 15.00  Citric Acid 2.50 3.96 1.88 1.98 0.902.50 0.60 Optical Brightener 1 1.00 0.80 0.10 0.30 0.05 0.50  0.001Optical Brightener 3  0.001 0.05 0.01 0.20 0.50 — 1.00 Sodium formate1.60 0.09 1.20 0.04 1.60 1.20 0.20 DTI 0.32 0.05 — 0.60 — 0.60 0.01Sodium hydroxide 2.30 3.80 1.70 1.90 1.70 2.50 2.30 Monoethanolamine1.40 1.49 1.00 0.70 — — — Diethylene glycol 5.50 — 4.10 — — — — Chelant1 0.15 0.15 0.11 0.07 0.50 0.11 0.80 4-formyl-phenylboronic acid — — — —0.05 0.02 0.01 Sodium tetraborate 1.43 1.50 1.10 0.75 — 1.07 — Ethanol1.54 1.77 1.15 0.89 — 3.00 7.00 Polymer 1 0.10 — — — — — 2.00 Polymer 20.30 0.33 0.23 0.17 — — — Polymer 3 — — — — — — 0.80 Polymer 4 0.80 0.810.60 0.40 1.00 1.00 — 1,2-Propanediol — 6.60 — 3.30 0.50 2.00 8.00Structurant 0.10 — — — — — 0.10 Perfume 1.60 1.10 1.00 0.80 0.90 1.501.60 Perfume encapsulate 0.10 0.05 0.01 0.02 0.10 0.05 0.10 Protease0.80 0.60 0.70 0.90 0.70 0.60 1.50 Mannanase 0.07 0.05  0.045 0.06 0.04 0.045 0.10 Amylase 1 0.30 — 0.30 0.10 — 0.40 0.10 Amylase 2 — 0.20 0.100.15 0.07 — 0.10 Xyloglucanase 0.20 0.10 — — 0.05 0.05 0.20 Lipase 0.400.20 0.30 0.10 0.20 — — Polishing enzyme — 0.04 — — —  0.004 — Nuclease0.05 — — — — —  0.003 Dispersin B — — — 0.05 0.03  0.001  0.001Liquitint ® V200 0.01 — — — — —  0.005 Leuco polymer 0.5  0.35 0.1  0.2 0.04 0.02 0.04 Dye control agent — 0.3  — 0.03 — 0.3  0.3  Water, dyes &minors Balance pH 8.2

Based on total cleaning and/or treatment composition weight. Enzymelevels are reported as raw material.

Examples 8 to 18 Unit Dose Compositions

These examples provide various formulations for unit dose laundrydetergents. Compositions 8 to 12 comprise a single unit dosecompartment. The film used to encapsulate the compositions ispolyvinyl-alcohol-based film.

8 9 10 11 12 Ingredients % weight LAS 19.09 16.76 8.59 6.56 3.44 AE3S1.91 0.74 0.18 0.46 0.07 AE7 14.00 17.50 26.33 28.08 31.59 Citric Acid0.6 0.6 0.6 0.6 0.6 C12-15 Fatty Acid 14.8 14.8 14.8 14.8 14.8 Polymer 34.0 4.0 4.0 4.0 4.0 Chelant 2 1.2 1.2 1.2 1.2 1.2 Optical Brightener 10.20 0.25 0.01 0.01 0.50 Optical Brightener 2 0.20 — 0.25 0.03 0.01Optical Brightener 3 0.18 0.09 0.30 0.01 — DTI 0.10 — 0.20 — — Glycerol6.1 6.1 6.1 6.1 6.1 Monoethanol amine 8.0 8.0 8.0 8.0 8.0Tri-isopropanol amine — — 2.0 — — Tri-ethanol amine — 2.0 — — — Cumenesulfonate — — — — 2.0 Protease 0.80 0.60 0.07 1.00 1.50 Mannanase 0.070.05 0.05 0.10 0.01 Amylase 1 0.20 0.11 0.30 0.50 0.05 Amylase 2 0.110.20 0.10 — 0.50 Polishing enzyme 0.005 0.05 — — — Nuclease 0.— 0.05 — —0.005 Dispersin B 0.010 0.05 0.005 0.005 — Cyclohexyl dimethanol — — —2.0 — Leuco polymer 0.6 0.3 1.0 0.1 0.4 Liquitint ® V200 — — 0.01 0.05 —Structurant 0.14 0.14 0.14 0.14 0.14 Perfume 1.9 1.9 1.9 1.9 1.9 Dyecontrol agent 0.1 0.3 0.2 0.5 0.3 Water and miscellaneous To 100% pH7.5-8.2

Based on total cleaning and/or treatment composition weight. Enzymelevels are reported as raw material.

In the following examples the unit dose has three compartments, butsimilar compositions can be made with two, four or five compartments.The film used to encapsulate the compartments is polyvinyl alcohol.

Base compositions 13 14 15 16 Ingredients % weight HLAS 26.82 16.35 7.503.34 AE7 17.88 16.35 22.50 30.06 Citric Acid 0.5 0.7 0.6 0.5 C12-15Fatty acid 16.4 6.0 11.0 13.0 Polymer 1 2.9 0.1 — — Polymer 3 1.1 5.12.5 4.2 Cationic cellulose polymer — — 0.3 0.5 Polymer 6 — 1.5 0.3 0.2Chelant 2 1.1 2.0 0.6 1.5 Optical Brightener 1 0.20 0.25 0.01 0.005Optical Brightener 3 0.18 0.09 0.30 0.005 DTI 0.1 — 0.05 — Glycerol 5.35.0 5.0 4.2 Monoethanolamine 10.0 8.1 8.4 7.6 Polyethylene glycol — —2.5 3.0 Potassium sulfite 0.2 0.3 0.5 0.7 Protease 0.80 0.60 0.40 0.80Amylase 1 0.20 0.20 0.200 0.30 Polishing enzyme — — 0.005 0.005 Nuclease0.05 — — — Dispersin B — 0.010 0.010 0.010 MgCl₂ 0.2 0.2 0.1 0.3Structurant 0.2 0.1 0.2 0.2 Acid Violet 50 0.04 0.03 0.05 0.03Perfume/encapsulates 0.10 0.30 0.01 0.05 Dye control agent 0.2 0.03 0.4— Solvents and misc. To 100% pH 7.0-8.2 Finishing compositions 17 18Compartment A B C A B C Volume of each compartment 40 ml 5 ml 5 ml 40 ml5 ml 5 ml Ingredients Active material in Wt. % Perfume 1.6 1.6 1.6 1.61.6 1.6 Liquitint ® V200 0 0.006 0 0 0.004 — Leuco polymer 0.2 0.4 — —TiO2 — — 0.1 — 0.1 Sodium Sulfite 0.4 0.4 0.4 0.1 0.3 0.3 Polymer 5 — 2— — Hydrogenated castor oil 0.14 0.14 0.14 0.14 0.14 0.14 BaseComposition 13, 14, 15 Add to 100% or 16

Based on total cleaning and/or treatment composition weight, enzymelevels are reported as raw material.

-   AE1.8S is C₁₂₋₁₅ alkyl ethoxy (1.8) sulfate-   AE3S is C₁₂₋₁₅ alkyl ethoxy (3) sulfate-   AE7 is C₁₂₋₁₃ alcohol ethoxylate, with an average degree of    ethoxylation of 7-   AE8 is C₁₂₋₁₃ alcohol ethoxylate, with an average degree of    ethoxylation of 8-   AE9 is C₁₂₋₁₃ alcohol ethoxylate, with an average degree of    ethoxylation of 9-   Amylase 1 is Stainzyme®, 15 mg active/g, supplied by Novozymes-   Amylase 2 is Natalase®, 29 mg active/g, supplied by Novozymes-   Xyloglucanase is Whitezyme®, 20 mg active/g, supplied by Novozymes-   Chelant 1 is diethylene triamine pentaacetic acid-   Chelant 2 is 1-hydroxyethane 1,1-diphosphonic acid-   Dispersin B is a glycoside hydrolase, reported as 1000 mg active/g-   DTI is either poly(4-vinylpyridine-1-oxide) (such as Chromabond    5-403E®), or poly(1-vinylpyrrolidone-co-1-vinylimidazole) (such as    Sokalan HP56®).-   Dye control agent Dye control agent in accordance with the    invention, for example Suparex® O.IN (M1), Nylofixan® P (M2),    Nylofixan® PM (M3), or Nylofixan® HF (M4)-   HSAS is mid-branched alkyl sulfate as disclosed in U.S. Pat. No.    6,020,303 and U.S. Pat. No. 6,060,443.-   LAS is linear alkylbenzenesulfonate having an average aliphatic    carbon chain length C₉-Cis (HLAS is acid form).-   Leuco colorant Any suitable leuco colorant or mixtures thereof    according to the instant invention.-   Lipase is Lipex®, 18 mg active/g, supplied by Novozymes-   Liquitint® V200 is a thiophene azo dye provided by Milliken-   Mannanase is Mannaway®, 25 mg active/g, supplied by Novozymes-   Nuclease is a Phosphodiesterase SEQ ID NO 1, reported as 1000mg    active/g-   Optical Brightener 1 is disodium    4,4′-bis{[4-anilino-6-morpholino-s-triazin-2-yl]-amino}-2,2′-stilbenedisulfonate

Optical Brightener 2 is disodium 4,4′-bis-(2-sulfostyryl)biphenyl(sodium salt)

-   Optical Brightener 3 is Optiblanc SPL10® from 3V Sigma-   Perfume encapsulate is a core-shell melamine formaldehyde perfume    microcapsules.-   Polishing enzyme is Para-nitrobenzyl esterase, reported as 1000 mg    active/g-   Polymer 1 is    bis((C₂H₅O)(C₂H₄O)_(n))(CH₃)—N⁺—C_(x)H_(2x)—N⁺—(CH₃)-bis((C₂H₅O)(C₂H₄O)_(n)),    wherein n=20-30, x=3 to 8 or sulphated or sulfonated variants    thereof-   Polymer 2 is ethoxylated (EO₁₅) tetraethylene pentamine-   Polymer 3 is ethoxylated polyethylenimine-   Polymer 4 is ethoxylated hexamethylene diamine-   Polymer 5 is Acusol 305, provided by Rohm&Haas-   Polymer 6 is a polyethylene glycol polymer grafted with vinyl    acetate side chains, provided by BASF.-   Protease is Purafect Prime®, 40.6 mg active/g, supplied by DuPont-   Structurant is Hydrogenated Castor Oil

The dimensions and values disclosed herein are not to be understood asbeing strictly limited to the exact numerical values recited. Instead,unless otherwise specified, each such dimension is intended to mean boththe recited value and a functionally equivalent range surrounding thatvalue. For example, a dimension disclosed as “40 mm” is intended to mean“about 40 mm.”

Every document cited herein, including any cross referenced or relatedpatent or application and any patent application or patent to which thisapplication claims priority or benefit thereof, is hereby incorporatedherein by reference in its entirety unless expressly excluded orotherwise limited. The citation of any document is not an admission thatit is prior art with respect to any invention disclosed or claimedherein or that it alone, or in any combination with any other referenceor references, teaches, suggests or discloses any such invention.Further, to the extent that any meaning or definition of a term in thisdocument conflicts with any meaning or definition of the same term in adocument incorporated by reference, the meaning or definition assignedto that term in this document shall govern.

While particular embodiments of the present invention have beenillustrated and described, it would be obvious to those skilled in theart that various other changes and modifications can be made withoutdeparting from the spirit and scope of the invention. It is thereforeintended to cover in the appended claims all such changes andmodifications that are within the scope of this invention.

We claim:
 1. A leuco polymer comprising an alkoxylated polyethyleneiminecovalently bound to a leuco moiety, wherein at least a first portion ofnitrogen atoms of the alkoxylated polyethyleneimine have covalentlybound thereto a leuco moiety; at least a second portion of nitrogenatoms of the alkoxylated polyethyleneimine have covalently bound theretoa moiety selected from the group consisting of oxyalkylene moieties,polyoxyalkylene moieties, and mixtures thereof; and at least a thirdportion of nitrogen atoms of the alkoxylated polyethyleneimine havecovalently bound thereto a moiety selected from the group consisting ofan alkylene chain, an alkylene chain having covalently bound thereto aphenyl or naphthyl group, and mixtures thereof.
 2. The leuco polymer ofclaim 1, wherein the polyethyleneimine has from 6 to 100 nitrogen atoms.3. The leuco polymer of claim 1, wherein the polyethyleneimine has from12 to 40 nitrogen atoms.
 4. The leuco polymer of claim 1, wherein thealkylene chain has a pendent alkyl group covalently bound to thepolyethyleneimine by the reaction of an amine of the polyethyleneiminewith dialkyl sulfates, alcohols, alkyl halides, olefins, and carbonylcompounds.
 5. The leuco polymer of claim 1, wherein the alkylene chainhas a pendent phenyl group formed by the addition of an amine of thepolyethyleneimine to styrene oxide or alpha-methyl styrene oxide.
 6. Theleuco polymer of claim 1, wherein the leuco moiety is selected from thegroup consisting of diarylmethane leuco moieties, triarylmethane leucomoieties, oxazine moieties, thiazine moieties, hydroquinone moieties,and arylaminophenol moieties.
 7. The leuco polymer of claim 6, whereinthe leuco moiety is selected from the group consisting of triarylmethaneleuco moieties, hydroquinone moieties, and arylaminophenol moieties. 8.The leuco polymer of claim 1, wherein the leuco moiety is covalentlybound to the nitrogen atom of the alkoxylated polyethyleneimine byreacting the alkoxylated polyethyleneimine with a compound comprising aleuco moiety and an electrophilic moiety, wherein the electrophilicmoiety of the compound is selected from the group consisting ofsulfooxyethylsulfonyl moieties, vinylsulfonyl moieties, halotriazinylmoieties, quaternary ammoniumtriazinyl moieties, halopyrimidinylmoieties, halopyridazinyl moieties, haloquinoxalinyl moieties,halophthalazinyl moieties, bromoacrlyamidyl moieties, and benzothiazolylmoieties.
 9. The leuco polymer of claim 7, wherein the leuco moiety is aunivalent or polyvalent moiety derived by removal of one or morehydrogen atoms from a structure of Formula (I), (II), (III), (IV), or(V) below

wherein the ratio of Formula I-V to its oxidized form is at least 1:3;wherein each individual R_(o), R_(m) and R_(p) group on each of rings A,B and C is independently selected from the group consisting of hydrogen,deuterium and R⁵; wherein each R⁵ is independently selected from thegroup consisting of halogens, nitro, alkyl, substituted alkyl, aryl,substituted aryl, alkaryl, substituted alkaryl, —C(O)R¹, —C(O)OR¹,—C(O)O—, —C(O)NR¹R², —OC(O)R¹, —OC(O)OR¹, —OC(O)NR¹R², —S(O)₂R¹, —S(O)₂OR¹, —S(O)₂O—, —S(O)₂NR¹R², —NR¹C(O)R², —NR¹C(O)OR², —NR¹C(O)SR²,NR¹C(O)SR², —NR¹C(O)NR²R³, —OR¹, —NR¹R², —P(O)₂R¹, —P(O)(OR¹)_(2,)—P(O)(OR¹)O—, and —P(O)(O—)²; wherein at least one of the R_(o) andR_(m) groups on at least one of the three rings A, B or C is hydrogen;each R_(p) is independently selected from hydrogen, —OR¹ and —NR¹R²;wherein G is independently selected from the group consisting ofhydrogen, deuterium, C1-C16 alkoxide, phenoxide, bisphenoxide, nitrite,nitrile, alkyl amine, imidazole, arylamine, polyalkylene oxide, halides,alkylsulfide, aryl sulfide, and phosphine oxide; wherein R¹, R² and R³are independently selected from the group consisting of hydrogen, alkyl,substituted alkyl, aryl, substituted aryl, alkaryl, substituted alkaryl,and R⁴; R⁴ is a organic group composed of one or more organic monomerswith said monomer molecular weights ranging from 28 to 500; wherein eand f are independently integers from 0 to 4; wherein each R²⁰ and R²¹is independently selected from the group consisting of a halogen, anitro group, alkyl groups, substituted alkyl groups, —NC(O)OR¹,—NC(O)SR¹, —OR¹, and —NR¹R²; wherein each R²⁵ is independently selectedfrom the group consisting of a monosaccharide moiety, a disaccharidemoiety, an oligosaccharide moiety, a polysaccharide moiety, —C(O)R¹,—C(O)OR¹, —C(O)NR¹R²; wherein each R²² and R²³ is independently selectedfrom the group consisting of hydrogen, an alkyl group, and substitutedalkyl groups; wherein R³⁰ is positioned ortho or para to the bridgingamine moiety and is selected from the group consisting of —OR³⁸ and—NR³⁶R³⁷, wherein each R³⁶ and R³⁷ is independently selected from thegroup consisting of hydrogen, an alkyl group, a substituted alkyl group,an aryl group, a substituted aryl group, an acyl group, R⁴, —C(O)OR¹,—C(O)R¹, and —C(O)NR¹R²; wherein R³⁸ is selected from the groupconsisting of hydrogen, an acyl group, —C(O)OR¹, —C(O)R¹, and—C(O)NR¹R²; wherein g and h are independently integers from 0 to 4;wherein each R³¹ and R³² is independently selected from the groupconsisting of an alkyl group, a substituted alkyl group, an aryl group,a substituted aryl group, an alkaryl, substituted alkaryl, —C(O)R¹,—C(O)OR¹, —C(O)O—, —C(O)NR¹R², —OC(O)R¹, —OC(O)OR¹, —OC(O)NR¹R²,—S(O)₂R¹, —S(O)₂O R¹, —S(O)₂O —, —S(O)₂NR¹R², —NR¹C(O)R², —NR¹C(O)OR²,—NR¹C(O)SR², —NR¹C(O)NR²R³, —OR¹, —NR¹R², —P(O)₂R¹, —P(O)(OR¹)_(2,)—P(O)(OR¹)O—, and —P(O)(O—)_(2 ;) wherein —NR³⁴R³⁵ is positioned orthoor para to the bridging amine moiety and R³⁴ and R³⁵ are independentlyselected from the group consisting of hydrogen, an alkyl, a substitutedalkyl, an aryl, a substituted aryl, an alkaryl, a substituted alkaryl,and R4; wherein R³³ is independently selected from the group consistingof hydrogen, —S(O)₂R¹, —C(O)N(H)R¹; —C(O)OR¹; and —C(O)R¹; wherein wheng is 2 to 4, any two adjacent R³¹ groups may combine to form a fusedring of five or more members wherein no more than two of the atoms inthe fused ring may be nitrogen atoms; wherein X⁴° is selected from thegroup consisting of an oxygen atom, a sulfur atom, and NR⁴⁵; wherein R⁴⁵is independently selected from the group consisting of hydrogen,deuterium, an alkyl, a substituted alkyl, an aryl, a substituted aryl,an alkaryl, a substituted alkaryl, —S(O)₂OH, —S(O)₂O, —C(O)OR¹, —C(O)R¹,and —C(O)NR¹R²; wherein R⁴⁰ and R⁴¹ are independently selected from thegroup consisting of —OR¹ and —NR¹R²; wherein j and k are independentlyintegers from 0 to 3; wherein R⁴² and R⁴³ are independently selectedfrom the group consisting of an alkyl, a substituted alkyl, an aryl, asubstituted aryl, an alkaryl, a substituted alkaryl, —S(O)₂R¹,—C(O)NR¹R², —NC(O)OR¹, —NC(O)SR¹, —C(O)OR¹, —C(O)R¹, —OR¹, —NR¹R²;wherein R⁴⁴ is —C(O)R¹, —C(O)NR¹R², and —C(O)OR¹; wherein any chargepresent in any of the compounds is balanced with a suitableindependently selected internal or external counterion.
 10. The leucopolymer of claim 9, wherein the leuco moiety is a moiety of Formula (I).11. The leuco polymer of claim 10, wherein two R_(o) groups on differentA, B and C rings combine to form a fused ring of five or more members.12. The leuco polymer of claim 11, wherein the fused ring is six or moremembers and two R_(o) groups on different A, B and C rings combine toform an organic linker containing one or more heteroatoms.
 13. The leucopolymer of claim 12, wherein two R_(o) on different A, B and C ringscombine to form a heteroatom bridge selected from —O— and —S— to createa six member fused ring.
 14. The leuco polymer of claim 10, whereineither an R_(o) and R_(m) on the same ring or an R_(m) and R_(p) on thesame ring combine to form a fused aliphatic ring or fused aromatic ring.15. The leuco polymer of claim 10, wherein all four of the R_(o) andR_(m) groups on at least one of the three rings A, B or C are hydrogen.16. The leuco polymer of claim 10, wherein all of the R_(o) and R_(m)groups on all three rings A, B or C are hydrogen.
 17. The leuco polymerof claim 10, wherein all three R_(p) are —NR¹R².
 18. The leuco polymerof claim 1, comprising a polyoxyalkylene moiety.
 19. The leuco polymerof claim 18, wherein the polyoxyalkylene moiety comprises oxyethylenegroups, oxypropylene groups, and mixtures thereof.
 20. The leuco polymerof claim 19, wherein the polyoxyalkylene moiety contains from 5 to 50oxyalkylene repeat units.
 21. The leuco polymer of claim 20, wherein thepolyoxyalkylene moiety contains from 10 to 20 oxyalkylene repeat units.22. The leuco polymer of claim 1, wherein only one or two of thenitrogens of the polyethyleneimine are alkoxylated.
 23. The leucopolymer of claim 1, wherein only one leuco moiety is covalently bound tothe polyethyleneimine.